Molecular sieve intergrowths of cha and aft having an “sfw-GME tail,” methods of preparation and use

ABSTRACT

Molecular sieves comprising intergrowths of cha and aft having an “sfw-GME tail”, at least one structure directing agent (SDA) within the framework of the molecular sieve, an intergrowth of CHA and GME framework structures, cha cavities, and aft cavities are described. A first SDA comprising either an N,N-dimethyl-3,5-dimethylpiperidinium cation or a N,N-diethyl-2,6-dimethylpiperidinium cation is required. A second SDA, which can further be present, is a CHA or an SFW generating cation. The amount of the second SDA-2 used can change the proportion of the components in the cha-aft-“sfw-GME tail”. Activated molecular sieves formed from SDA containing molecular sieves are also described. Compositions for preparing these molecular sieves are described. Methods of preparing a SDA containing JMZ-11, an activated JMZ-11, and metal containing activated JMZ-11 are described. Methods of using activated JMZ-11 and metal containing activated JMZ-11 in a variety of processes, such as treating exhaust gases and converting methanol to olefins are described.

FIELD OF INVENTION

The present invention relates to molecular sieves comprisingintergrowths of cha and aft having an “sfw-GME tail”. These molecularsieves include as-made molecular sieves containing one or more structuredirecting agents (SDAs), as well as activated molecular sieves, which donot contain an SDA, and can be formed from an SDA containing molecularsieve. The invention also relates to methods of preparation of the SDAcontaining molecular sieves and activated molecular sieves, and methodsusing these activated molecular sieves as a catalyst.

BACKGROUND OF THE INVENTION

Molecular sieves are a commercially important class of materials thathave distinct crystal structures with defined pore structures that areshown by distinct X-ray diffraction (XRD) patterns. The crystalstructure defines cavities and channels/pores that are characteristic ofthe specific type of molecular sieve. This is usually described as theframework type or topological type. A full listing of framework types ismaintained by the IZA (International Zeolite Association)http://www.iza-structure.org/databases/. Such framework types ortopological types are not defined by composition, but only by thearrangement of the T-atoms (tetrahedral atoms) that bound thechannels/pores and cavities and make up a structure. A framework type ortopological type is unique and is provided with a unique three lettercode by the IZA.

During the formation and growth of a molecular sieve crystal, sometimesfaults occur that can initiate the growth of different structures withinthe bulk material. This can result in the appearance of a separate phaserecognized by XRD. This separate phase can be referred to as adisordered structure or an intergrowth. Disordered structures aredefined as structures possessing periodic ordering in dimensions lessthan 3, such as 2, 1, or zero-dimensions. This phenomenon is also calledstacking disorder of structurally invariant Periodic Building Units(PerBUs). In other words, disordered structures are those where thestacking sequence of the PerBU deviates from periodic ordering up torandom stacking sequences. Chemical disorder (i.e. different cations ona particular site), dynamic disorder (i.e rotational disorder oftemplate molecules) and structural disorder (i.e. disordered moleculesin the cavities of zeolite frameworks) are excluded from thisdefinition. The physical chemical properties and the catalytic behaviourof a disordered structure might be different to those of the orderedcounterpart. Examples include CHA/AEI composed of layers of doublesix-member rings (M. Janssen, A. Verberckmoes, M. Mertens, A. Bons, W.Mortier, ExxonMobile Chemical Europe Inc. EP patent no. 1365 992 B1,2007. W. A. Slawinski, D. S. Wragg, D. Akporiaye, H. Fjellvag,Microporous Mesoporous Mater., 2014, 195, 311-318), EMT/FAU composed ofsod cages linked through double T6-rings into a hexagonal layer (J. M.Newsam, M. M. J. Treacy, D. E. W. Vaughan, K. G. Strohmaier, W. J.Mortier, Chem. Commun., 1989, 493-495), LOV/VSV/RSN composed of T9units: two 4-rings connected through a single T atom related by puretranslations along a- and b-axes (S. Merlino, Eur. J. Miner., 1990, 2,809-817. C. Röhrig, H. Gies, B. Marler, Zeolites, 1994, 14, 498-503. C.Röhrig, H. Gies, Angew. Chem. Int. Ed. Engl., 1995, 34, 63-65) etc.Further Examples of disorder in zeolite frameworks are reported in thedatabase of zeolite structures(http://europe.iza-structure.org/IZA-SC/intergrowth_Table.html). Thesynthetic conditions, the nature of the metal cations, the shape andsize of the SDAs employed for the synthesis of structures belonging to agiven family, may affect the ordered arrangement of the building units,resulting in the formation of intergrowth and stacking disorderstructures.

The new intergrowth zeolites herein described are related to the ABC-6family of structures, in particular those containing only doublesix-rings (D6Rs)(http://europe.iza-structure.org/IZA-SC/intergrowth_families/ABC_6.pdf).The ABC-6 structures are built up from 6Rs with different stackingarrangements along one axis and linked by 4Rs. The 6R units can becentred on three different positions along the hexagonal ab-plane: A (0,0, 0), B (2/3, 1/3, 0) and C (1/3, 2/3, 0).

The molecular sieves synthesised and identified as member of thedisordered ABC-6 family consisting only of double-6-rings are: ZK-14 [G.H. Kuehl. In: Molecular Sieves S. C. I., London, 1967, p 85]; Babelite[R. Szostak and K. P. Lillerud, J. Chem. Soc. Chem. Commun. 1994, (20),2357-2358]; Linde D [K. P. Lillerud, R. Szostak and A. Long, J. Chem.Soc. Faraday Trans. 1994, 90, 1547-1551; GB Patent 868, 649]; Phi [K. P.Lillerud, R. Szostak and A. Long, J. Chem. Soc. Faraday Trans. 1994, 90,1547-1551; U.S. Pat. No. 4,124,686]; LZ-276 [G. W. Skeels, M. Sears, C.A. Bateman, N. K. McGuire, E. M. Flanigen, M. Kumar, R. M. Kirchner,Micropor. Mesopor. Mater. 30, 335 (1999); U.S. Pat. No. 5,248,491];LZ-277 [G. W. Skeels, M. Sears, C. A. Bateman, N. K. McGuire, E. M.Flanigen, M. Kumar, R. M. Kirchner, Micropor. Mesopor. Mater. 30, 335(1999); U.S. Pat. No. 5,192,522]; SAPO AFX/CHA [U.S. Pat. No.7,906,099]; SSZ-52 [D. Xie, L. B. McCusker, C. Baerlocher, S. I. Zones,W. Wan, X. Zou, J. Am. Chem. Soc. 2013, 135(28), 10519-24; U.S. Pat. No.6,379,531]; ZTS-1 and ZTS-2 [Y. Naraki, K. Ariga, K. Nakamura, K.Okushita, T. Sano, Microporous Mesoporous Mater. (2017) 254, 160-169; JPPatent 2017065943]; faulted CHA-type zeolites [J. Kim, D. H. Kim,Microporous Mesoporous Mater. 2018, 256, 266-274]; faulted-GME [U.S.Pat. No. 9,643,853]; SSZ-52x [U.S. Pat. No. 10,150,676]; GME/CHA [WO2018/086974].

WO 2018/086974 discloses a method of preparing a series of zeolitesbelonging to the ABC-6 framework family with disorder in the ABCstacking sequence and with silica to alumina ratio in the range 8-60.The diffraction peaks in claim 3 and the relative Examples reportedallow to classify these zeolites as stochastic CHA-GME intergrowths.

Molecular sieves have numerous industrial applications, and molecularseizes having certain frameworks, such as CHA, are known to be effectivecatalyst for treating combustion exhaust gas in industrial applicationsincluding internal combustion engines, gas turbines, coal-fired powerplants, and the like. In one Example, nitrogen oxides (NOx) in theexhaust gas may be controlled through a so-called selective catalyticreduction (SCR) process whereby NOx compounds in the exhaust gas arecontacted with a reducing agent in the presence of a zeolite catalyst.In another Example, molecular sieves having the CHA framework type havefound application in the conversion of methanol to olefins (MTO)catalysis.

There is a need to develop new molecular sieves having the basicstructure of known molecular sieves, where minor changes in thestructure can affect one or more of the catalytic properties of themolecular sieve. In some cases, while minor changes in the structure maynot be discernible using normally used analytical techniques, thecatalytic activity of the structurally modified zeolite may be improvedrelative to very closely related analogous zeolites. Unexpectedimprovements in the catalytic activity of such structurally modifiedmolecular sieves can allow for the compositions of exhaust gases fromengines to meet various regulatory requirements.

SUMMARY OF THE INVENTION

In a first aspect of the invention, provided are a family (JMZ-11) ofmolecular sieves comprising intergrowths of cha and aft having an“sfw-GME tail”, where the molecular sieves comprise one or morestructure direct agents, hereinafter called “the molecular sieves” or“these molecular sieves”. The “sfw-GME tail” can be determined byanalysis using a Reichweite 2 DIFFaX model.

Four subgroups of the JMZ-11 family of molecular sieves, JMZ-11A,JMZ-11B, JMZ-11C and JMZ-11D, comprising these intergrowths aredescribed below.

JMZ-11A comprises a structure direct agent (SDA-1), where SDA-1 is aN,N-dimethyl-3,5-dimethylpiperidinium cation, cha cavities, aft cavitiesand an “sfw-GME” tail, wherein the cha cavities are present at about 45to about 65%, preferably about 54%, of the cavities in the tail, the aftcavities are present at about 18 to about 28%, preferably about 23% ofthe cavities in the tail, and the remaining about 7 to about 37%,preferable about 23%, of larger cavities in the “sfw-GME” tail. The gmecavities associated with the aft and larger cavities are not included inthese figures. The “sfw-GME” tail accounts for about 35-80% of thevolume of the molecular sieve or the molecular sieve particle,preferably about 68%. JMZ-11A has a monotonically decreasingdistribution of cavity sizes, but it cannot be described as a stochasticCHA-GME intergrowth.

JMZ-11B comprises a structure direct agent (SDA-1), where SDA-1 is aN,N-diethyl-2,6-dimethylpiperidinium cation, cha cavities, aft cavitiesand an “sfw-GME” tail, wherein the cha cavities are present at about 55to about 75%, preferably about 65%, of the cavities in the tail, the aftcavities are present at about 0 to about 10%, preferably about 5% of thecavities in the tail, and the remaining about 15 to about 45%,preferable about 30%, of larger cavities in the “sfw-GME” tail. The gmecavities associated with the aft and larger cavities are not included inthese figures. The “sfw-GME” tail accounts for about 40-80% of thevolume of the molecular sieve or the molecular sieve particle,preferably about 64%. JMZ-11B has a monotonically decreasingdistribution of cavity sizes, but it cannot be described as a stochasticCHA-GME intergrowth.

JMZ-11C comprises two structure direct agents, anN,N-dimethyl-3,5-dimethylpiperidinium cation and a1,3-bis(1-adamantyl)imidazolium cation, cha cavities, aft cavities andan “sfw-GME” tail, wherein the cha cavities are present at about 30 toabout 45%, preferably about 39%, of the cavities in the tail, the aftcavities are present at about 45 to about 65%, preferably about 54% ofthe cavities in the tail, and the remaining about 2 to about 20%,preferable about 7%, of larger cavities in the “sfw-GME” tail. The gmecavities associated with the aft and larger cavities are not included inthese figures. The “sfw-GME” tail accounts for about 5-45% of the volumeof the molecular sieve or the molecular sieve particle, preferably about23%. JMZ-11C has a monotonically decreasing distribution of cavitysizes, but it cannot be described as a stochastic CHA-GME intergrowth.

JMZ-11D comprises two structure direct agents, anN,N-dimethyl-3,5-dimethylpiperidinium cation and atrimethyladmandylammonium cation, cha cavities, aft cavities and an“sfw-GME” tail, wherein the cha cavities are present at about 55 toabout 75%, preferably about 65%, of the cavities in the tail, the aftcavities are present at about 7 to about 17%, preferably about 12% ofthe cavities in the tail, and the remaining about 8 to about 38%,preferable about 23%, of larger cavities in the “sfw-GME” tail. The gmecavities associated with the aft and larger cavities are not included inthese figures. The “sfw-GME” tail accounts for about 50-90% of thevolume of the molecular sieve or the molecular sieve particle,preferably about 75%. JMZ-11D has a monotonically decreasingdistribution of cavity sizes, but it cannot be described as a stochasticCHA-GME intergrowth.

The molecular sieves described herein can be an aluminosilicate or ametal-substituted aluminosilicate. Preferably, the molecular sieve is analuminosilicate.

These molecular sieves can comprise phosphorus in the framework. Thesemolecular sieves can be an aluminophosphate (APO), a metal-substitutedaluminophosphate (MeAlPO), a silico-aluminophosphate (SAPO), or a metalsubstituted silico-aluminophosphate.

These molecular sieves can comprise at least one metal within theframework where the metal is from one of the groups IIIA, IB, IIB, VA,VIA, VIIA, VIIIA of the Periodic Table, and combinations thereof.Preferably the metal is one or more of cerium, chromium, cobalt, copper,iron, magnesium, manganese, molybdenum, nickel, palladium, platinum,rhodium, titanium, tungsten, vanadium and zinc. More preferably themetal is one or more of cobalt, copper, iron, manganese and zinc.

In a second aspect of the invention, an activated H-form hereinaftercalled “the activated molecular sieves” or “these activated molecularsieves” of the molecular sieves of the first aspect of the invention aredescribed.

The activated H-form of these molecular sieves can be an aluminosilicateor a metal-substituted aluminosilicate. Preferably, the activated H-formof These molecular sieves is an aluminosilicate.

The activated H-form of these molecular sieves can contain a phosphorusthin the framework. These activated H-form of these molecular sieves canbe an aluminophosphate (AlPO), a metal-substituted aluminophosphate(MeAlPO), a silico-aluminophosphate (SAPO), or a metal substitutedsilico-aluminophosphate.

The activated H-form of these molecular sieves can comprise at least onemetal within the framework where the metal is selected from at least oneof the metals of groups IIIA, IB, IIB, VA, VIA, VIIA, and VIIIA of thePeriodic Table, and combinations thereof. Preferably the metal iscerium, chromium, cobalt, copper, iron, magnesium, manganese,molybdenum, nickel, palladium, platinum, rhodium, titanium, tungsten,vanadium or zinc. More preferably the metal is cobalt, copper, iron,manganese, or zinc.

The activated H-form of these molecular sieves can comprise at least oneextra-framework metal selected from the group consisting of Ag, Au, Ce,Co, Cr, Cu, Fe, Ga, In, Ir, Mn, Mo, Ni, Os, Pd, Pt, Re, Rh, Ru, Sn andZn, preferably Cu, Fe, Co and Ni, more preferably Cu and Fe, mostpreferably Cu.

In a third aspect of the invention, a catalyst comprises an activatedH-form of one or more of the molecular sieves of the second aspect ofthe invention and at least one extra-framework metal selected from thegroup consisting of Ag, Au, Ce, Co, Cr, Cu, Fe, Ga, In, Ir, Mn, Mo, Ni,Os, Pd, Pt, Re, Rh, Ru, Sn and Zn, preferably Cu, Fe, Co and Ni, morepreferably Cu and Fe, most preferably Cu.

The activated H-form molecular sieve in the catalyst can comprise about0.1 to about 5 weight percent of at least one extra-framework metal.

The activated H-form of these molecular sieves can be an aluminosilicateor a metal-substituted aluminosilicate, preferably an aluminosilicate.

The activated H-form of these molecular sieves can contain phosphorus inthe framework. These activated H-form of these molecular sieves can bean aluminophosphate (AlPO), a metal-substituted aluminophosphate(MeAlPO), a silico-aluminophosphate (SAPO), or a metal substitutedsilico-aluminophosphate.

The activated H-form of these molecular sieves can comprise at least onemetal within the framework where the metal is selected from at least oneof the metals of groups IIIA, IB, IIB, VA, VIA, VIIA and VIIIA of thePeriodic Table, and combinations thereof. Preferably the metal is one ormore of cerium, chromium, cobalt, copper, iron, magnesium, manganese,molybdenum, nickel, palladium, platinum, rhodium, titanium, tungsten,vanadium and zinc, more preferably cobalt, copper, iron, manganese andzinc.

In a fourth aspect of the invention, a catalyst article for treatingexhaust gas comprises a catalyst comprising an activated H-form of oneor more of the molecular sieves of the second aspect of the inventionand at least one extra-framework metal selected from the groupconsisting of Ag, Au, Ce, Co, Cr, Cu, Fe, Ga, In, Ir, Mn, Mo, Ni, Os,Pd, Pt, Re, Rh, Ru, Sn and Zn, preferably Cu, Fe, Co and Ni, morepreferably Cu and Fe, most preferably Cu.

The activated H-form of these molecular sieves in the catalyst cancomprise about 0.1 to about 5 weight percent of at least oneextra-framework metal.

The catalyst can be disposed on and/or within a porous substrate,preferably a flow through or wall-flow filter.

In a fifth aspect of the invention, systems for treating exhaust gasgenerated by combustion process, such as from an internal combustionengine (whether mobile or stationary), a gas turbine, coal or oil firedpower plants, and the like, comprise a catalyst article comprising anactivated H-form of one or more of the molecular sieves of the secondaspect of the invention and at least one extra-framework metal. Suchsystems include a catalytic article comprising an activated molecularsieve, described herein, and can include at least one additionalcomponent for treating the exhaust gas, wherein the catalytic articleand at least one additional component are designed to function as acoherent unit.

An exhaust system for treating exhaust gases from an engine cancomprise: (a) a catalyst article comprising one or more of an activatedH-form of one or more of the molecular sieves of the second aspect ofthe invention and at least one extra-framework metal selected from thegroup consisting of Ag, Au, Ce, Co, Cr, Cu, Fe, Ga, In, Ir, Mn, Mo, Ni,Os, Pd, Pt, Re, Rh, Ru, Sn and Zn, preferably Cu, Fe, Co and Ni, morepreferably Cu and Fe, most preferably Cu, disposed downstream from theengine; (b) a source of a reductant, such as ammonia or urea upstream ofsaid catalyst article; and (c) an exhaust gas conduit for carrying theexhaust gases from the engine to said catalyst article.

In some embodiments, the activated H-form of these molecular sieves canbe an SCR or an ammonia oxidation component.

A system can comprise a catalytic article comprising one or more ofthese molecular sieves or one or more of a metal containing activatedmolecular sieves, a conduit for directing a flowing exhaust gas, and asource of nitrogenous reductant disposed upstream of the catalyticarticle. The system can include a controller for metering thenitrogenous reductant into the flowing exhaust gas only when it isdetermined that one or more activated molecular sieves or one or moremetal containing activated molecular sieves is capable of catalyzingNO_(x) reduction at or above a desired efficiency over a specifictemperature range, such as at above 100° C., above 150° C. or above 175°C. The metering of the nitrogenous reductant can be arranged such that60% to 200% of theoretical ammonia is present in exhaust gas enteringthe SCR catalyst calculated at 1:1 NH₃/NO and 4:3 NH₃/NO₂.

The system can comprise an oxidation catalyst (e.g., a diesel oxidationcatalyst (DOC)) for oxidizing nitrogen monoxide in the exhaust gas tonitrogen dioxide can be located upstream of a point of metering thenitrogenous reductant into the exhaust gas. The oxidation catalyst canbe adapted to yield a gas stream entering the SCR molecular sievecatalyst having a ratio of NO to NO₂ of from about 4:1 to about 1:3 byvolume, e.g. at an exhaust gas temperature at oxidation catalyst inletof 250° C. to 450° C. The oxidation catalyst can include at least oneplatinum group metal (or some combination of these), such as platinum,palladium, or rhodium, coated on a flow-through monolith substrate. Theat least one platinum group metal can be platinum, palladium or acombination of both platinum and palladium. The platinum group metal canbe supported on a high surface area washcoat component such as alumina,a zeolite, silica, non-zeolite silica alumina, ceria, zirconia, titaniaor a mixed or composite oxide containing both ceria and zirconia.

A suitable filter substrate can be located between the oxidationcatalyst and the SCR catalyst. Filter substrates can be selected fromany of those mentioned above, e.g. wall flow filters. Where the filteris catalyzed, e.g. with an oxidation catalyst of the kind discussedabove, preferably the point of metering nitrogenous reductant is locatedbetween the filter and the molecular sieve catalyst. Alternatively, ifthe filter is un-catalyzed, the means for metering nitrogenous reductantcan be located between the oxidation catalyst and the filter.

In a sixth aspect of the invention, a method for synthesizing an SDAcontaining molecular sieve of the first aspect of the inventioncomprises:

-   -   a. forming a reaction mixture comprising: (i) at least one        source of aluminum, (ii) at least one source of silicon, (iii)        at least one source of alkaline or alkaline-earth cations        and (iv) one or more structure directing agents;    -   b. heating the reaction mixture;    -   c. forming molecular sieve crystals having an intergrowth and        the structure directing agent as described herein, and    -   d. recovering at least a portion of the molecular sieve crystals        from the reaction mixture.

The SDA for JMZ-11A comprises an N,N-dimethyl-3,5-dimethylpiperidiniumcation. The SDA for JMZ-11B comprises anN,N-diethyl-2,6-dimethylpiperidinium cation. The SDA for JMZ-11Ccomprises an N,N-dimethyl-3,5-dimethylpiperidinium cation and a1,3-bis(1-adamantyl)imidazolium cation. The SDA for JMZ-11D comprises anN,N-dimethyl-3,5-dimethylpiperidinium cation and atrimethyladmandylammonium cation.

The at least one source of aluminum can comprise aluminum alkoxides,aluminum phosphates, aluminum hydroxide, sodium aluminate,pseudoboehmite, hydrated alumina, organo alumina, colloidal alumina,zeolite Y and mixtures thereof.

The at least one source of silicon can be an alkoxide, colloidal silica,silica gel, a silicate, a tetraalkyl orthosilicate, or an aqueouscolloidal suspension of silica.

The source of alkaline or alkaline-earth cations may be any source ofthese elements, preferably selected from a source of Na, K andcombinations thereof.

The cation of the structure directing agent can be associated with ananion selected from the group consisting of acetate, bicarbonate,bromide, carbonate, carboxylate, chloride, fluoride, hydroxide, iodide,sulfate and tetrafluoroborate. Preferably the anion is hydroxide.

The reaction mixture can have a molar compositional ratio of:

Components Ratio Preferred Ratio MeO₂/A₂O₃ 10-100 20-50 (SDA-1 + SDA-2 +SDA-3)/A₂O₃ 1-6  1.0-3.0 SDA-2/SDA-1  0-100 0.00-15.0 SDA-3/SDA-1  0-1000.00-15.0 X₂O/A₂O₃ 5.0-20.0 7.5-15  [OH⁻]/A₂O₃ 10.0-30.0  16.0-30 H₂O/A₂O₃ 100-2000 200-800

-   -   where Me is Si, Ge, Sn, Ti or combinations thereof and is        calculated as being in the oxide form (MO₂); A is Al, Fe, Cr, B,        Ga or combinations thereof and is calculated as being in the        oxide form (A₂O₃); X is Na, K or a combination thereof and is        calculated as being in the oxide form (X₂O); [OH-] is calculated        being as the sum of hydroxide ions brought by all components;        SDA-1 is an N,N-dimethyl-3,5-dimethylpiperidinium cation or an        N,N-diethyl-2,6-dimethylpiperidinium cation, SDA-2 is a CHA        generating SDA, such as a trimethyladmandylammonium cation, a        tetraethylammonium cation, a trimethylbenzylammonium cation, a        trimethylcyclohexylammonium cation or a        trimethyl(cyclohexylmethyl)ammonium or a phenyltrimethylammonium        cation and SDA-3 is a AFX generating SDA, such as a        1,3-bis(1-adamantyl)imidazolium,        1,1-(butane-1,4-diyl)bis-(quinuclidin-1-ium),        1,1-(pentane-1,5-diyl)bis-(quinuclidin-1-ium),        1,1′-(1,4-butanediyl)bis(4-aza-1-azoniabicyclo[2.2.2]octane),        1,1′-(1,5-pentanediyl)bis(4-aza-1-azoniabicyclo[2.2.2]octane).

The reaction mixture can further comprise from about 0.1 to about 10%w/w of seed crystals, wherein the seed crystals comprise a crystallinemolecular sieve having an AEI, AFX, AFT, CHA, GME or an SFW frameworkand/or an intergrowth having a JMZ-11 framework.

In a seventh aspect of the invention, methods of synthesizing anactivated molecular sieve of the second aspect of the invention from amolecular sieve comprising structure directing agents (SDAs) of thefirst aspect of the invention, are described. An activated molecularsieve lacks the structure directing agent(s) that is present in themolecular sieve of the first aspect of the invention. Molecular sievescomprising structure directing agents (SDAs) can have the SDAs removedby calcination, treatment with compound that can react with andpreferably decompose the SDA, such as a peroxide.

In an eighth aspect of the invention, a composition for manufacturingSDA containing molecular sieves of the first aspect of the inventioncomprises the following materials in the corresponding ratios:

The reaction mixture can have a molar compositional ratio of:

Components Ratio Preferred Ratio MeO₂/A₂O₃ 10-100 20-50 (SDA-1 + SDA-2 +SDA-3)/A₂O₃ 1-6  1.0-3.0 SDA-2/SDA-1  0-100 0.00-15.0 SDA-3/SDA-1  0-1000.00-15.0 X₂O/A₂O₃ 5.0-20.0 7.5-15  [OH⁻]/A₂O₃ 10.0-30.0  16.0-30 H₂O/A₂O₃ 100-2000 200-800

-   -   where Me is Si, Ge, Sn, Ti or combinations thereof and is        calculated as being in the oxide form (MO₂); A is Al, Fe, Cr, B,        Ga or combinations thereof and is calculated as being in the        oxide form (A₂O₃); X is Na, K or a combination thereof and is        calculated as being in the oxide form (X₂O); [OH⁻] is calculated        being as the sum of hydroxide ions brought by all components;        SDA-1 is an N,N-dimethyl-3,5-dimethylpiperidinium cation or an        N,N-diethyl-2,6-dimethylpiperidinium cation, SDA-2 is a CHA        generating SDA, such as a trimethyladmandylammonium cation, a        tetraethylammonium cation, a trimethylbenzylammonium cation, a        trimethylcyclohexylammonium cation or a        trimethyl(cyclohexylmethyl)ammonium or a phenyltrimethylammonium        cation and SDA-3 is a AFX generating SDA, such as a        1,3-bis(1-adamantyl)imidazolium,        1,1-(butane-1,4-diyl)bis-(quinuclidin-1-ium),        1,1-(pentane-1,5-diyl)bis-(quinuclidin-1-ium),        1,1′-(1,4-butanediyl)bis(4-aza-1-azoniabicyclo[2.2.2]octane),        1,1′-(1,5-pentanediyl)bis(4-aza-1-azoniabicyclo[2.2.2]octane).

The composition can further comprise from about 0.1 to about 10% w/w ofseed crystals, wherein the seed crystals comprise a crystallinemolecular sieve having an AEI, AFX, AFT, CHA, GME or an SFW frameworkand/or an intergrowth having a JMZ-11, JMZ-11B or JMZ-11C framework.

In a ninth aspect of the invention, provided are methods of making anactivated molecular sieve of the second aspect of the invention from amolecular sieve containing SDAs and alkali metal cations of the firstaspect of the invention. Molecular sieves of the present invention maybe a Na-form zeolite, a K-form zeolite, or a combined Na, K-form and thelike, or may be an H-form zeolite, an ammonium-form zeolite, or ametal-exchanged zeolite. Methods of making an activated molecular sieveof the second aspect of the invention from a molecular sieve comprisingSDAs and alkali metal cations of the first aspect of the invention canuse typical ion exchange techniques what involve contacting themolecular sieve with a solution containing a salt of the desiredreplacing cation or cations. Ion exchange occurs post-synthesis and cantake place either before or after the molecular sieve is calcined.

In a tenth aspect of the invention, provided are methods for treating anexhaust gas from an engine by contacting the exhaust gas with anactivated molecular sieve of the second aspect of the invention asherein described.

A method for treating an exhaust gas comprises contacting a combustionexhaust gas containing NO_(x) and/or NH₃ with an activated H-form of amolecular sieve of the second aspect of the invention as describedherein to selectively reduce at least a portion of the NO_(x) into N₂and H₂O and/or oxidize at least a portion of the NH₃.

A method for treating an exhaust gas comprising contacting a combustionexhaust gas containing NO_(x) with a passive NO_(x) absorber comprisingan activated H-form of a molecular sieve of the second aspect of theinvention, as described herein.

In an eleventh aspect of the invention, provided is a method ofconverting methanol to an olefin (MTO) by contacting methanol with anactivated H-form of a molecular sieve of the second aspect of theinvention as herein described.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a powder XRD pattern of SDA containing (as-made) JMZ-11A withnormalized intensities.

FIG. 2 is a powder XRD pattern of activated (calcined) H-JMZ-11A withnormalized intensities.

FIG. 3 is a powder XRD pattern of SDA containing (as-made) JMZ-11B withnormalized intensities.

FIG. 4 is a powder XRD pattern of activated (calcined) H-JMZ-11B withnormalized intensities.

FIG. 5 is a powder XRD pattern of SDA containing (as-made) JMZ-11C withnormalized intensities.

FIG. 6 is a powder XRD pattern of activated (calcined) H-JMZ-11C withnormalized intensities.

FIG. 7 is a powder XRD pattern of SDA containing (as-made) JMZ-11D withnormalized intensities.

FIG. 8 is a powder XRD pattern of activated (calcined) H-JMZ-11D withnormalized intensities.

FIG. 9 shows the powder XRD patterns of calcined H-JMZ-11A to H-JMZ11Dwith normalized intensities shown at from 7 to 13 degrees 2-theta.

FIG. 10 is a representation of the CHA building scheme from IZA.

FIG. 11 is a representation of the GME building scheme from IZA.

FIG. 12 is a transition probability matrix for a Reichweite 0 where thestacking probability of a layer is independent of the previous stacking.

FIG. 13 is a transition probability matrix for a Reichweite 1 where theprevious one 5 Angstrom thick layer influence the stacking probability.

FIG. 14 is a transition probability matrix for a Reichweite 2description where previous two 5 Angstrom thick layers influence thestacking probability.

FIG. 15 is a diagram showing the cage distribution for a simplestochastic CHA-GME framework intergrowth (equivalent to Reichweite 0).

FIG. 16 is a diagram showing the cage distribution for a simple “block”intergrowth of CHA and GME.

FIG. 17 is a diagram showing the cage distribution for acha-aft-“sfw-GME” tail intergrowths in Example 1 (JMZ-11A).

FIG. 18 to 21 show the cage distribution within JMZ-11A, JMZ-11B,JMZ-11C and JMZ-11D.

FIGS. 22-25 show the comparison between the experimental XRD patterns ofactivated JMZ-11A, JMZ-11B, JMZ-11C, and JMZ-11D and the DIFFaXsimulations carried out using the Reichweite 2 description.

FIG. 26 shows NO_(x) conversion profiles from fresh JMZ-11 samplesimpregnated with Cu.

FIG. 27 shows NO_(x) conversion profiles from aged JMZ-11 samplesimpregnated with Cu.

FIG. 28 shows N₂O production profiles from fresh JMZ-11 samplesimpregnated with Cu.

FIG. 29 shows N₂O production profiles from aged JMZ-11 samplesimpregnated with Cu.

DETAILED DESCRIPTION OF THE INVENTION

The following terms will be used throughout the specification and willhave the following meanings unless otherwise indicated.

As used in this specification and the appended claims, the singularforms “a”, “an” and “the” include plural referents unless the contextclearly indicates otherwise. Thus, for example, reference to “acatalyst” includes a mixture of two or more catalysts, and the like.

The term “about” means approximately and refers to a range that isoptionally ±25%, preferably ±10%, more preferably, ±5%, or mostpreferably ±1% of the value with which the term is associated.

The term “substantially similar”, when used to describe a comparison ofa diffraction pattern, means that the locations of one or more peaks, indegrees 2-theta, and the intensity of these peaks can vary based onexperimental variability due to the instrumentation used, the conditionsunder which the diffraction pattern was obtained, and impurities thatmay be present in a sample.

When a range, or ranges, for various numerical elements are provided,the range, or ranges, can include the values, unless otherwisespecified.

The term “stochastic” refers to a property that is randomly determined.It can have a random probability distribution or a pattern that may beanalyzed statistically but may not be predicted precisely.

A “molecular sieve” is a crystalline substance with pores of moleculardimensions that permit the passage of molecules below a certain size.The term “molecular sieve” encompasses both zeolites and zeotypes.Zeolites are microporous crystalline aluminosilicates, composed of TO₄tetrahedra (T=Si, Al) with O atoms connecting neighboring tetrahedra.Zeolites are materials having an alumina and silicate framework andinclude both aluminosilicates and metal-substituted aluminosilicates.Zeotypes are aluminophosphates (AlPO), metal-substitutedaluminophosphates (MeAlPO), silico-aluminophosphates (SAPO), and metalsubstituted silico-aluminophosphates. The term “molecular sieve” canalso include mixture of two or more of the above materials.

The term “framework type” is used in the sense described in the “Atlasof Zeolite Framework Types,” Sixth Revised Edition, Elsevier, 2007.

The fundamental or primary building unit (PBU) in a zeolite structure isthe TO₄ tetrahedron. Zeolite structure types can be described accordingto the structural building units within the framework, the pore openingsand dimensionality of the channel system, and in the stacking ofdifferent polyhedral cage units. Structural building units, also knownas secondary building units (SBUs), consist of tetrahedral units boundtogether into rings or cages by sharing a vertex for each pair oftetrahedra, via non-linear oxygen bridges. These SBUs are named in termsof the number of T-atoms they contain, for example a six-membered ring,6R, or as pairs of rings denoted as double n-rings, (for example, doublesix-rings, D6R). A three-dimensional framework can be built byassembling only one kind of SBU. However, the structure of some zeolitesis better described by using finite structural subunits (SSUs) which arepolyhedral forms characterized by a quite complex symmetry, i.e.sodalite or gmelinite cages. The SSUs represent a structural feature.Therefore, they are not SBUs because very often the framework cannot beconstructed from SSUs alone. Frequently, SSUs need to share corners,faces or edges to complete the framework. Another way to describe cagesin the framework structure is to write them in terms of the rings thatmake up the faces of the cage, so that a D6R is expressed as [4⁶ 6²].Moreover, many structures can be described in terms of layers stackedupon each other, so-called infinite layers. SBUs and SSUs as such, arenot meant to describe precursors from which the zeolite grows but maygive clues to choose specific cations or structure-directing agentssuitable to favor the formation of specific units and consequently ofthe desired framework structure.

The structural aspect of great importance in zeolites is the presence ofcavities and channels connected to each other by means of windows toform a porous network within the structure. A pore is an opening thatgoes from one side of a crystal to another side of the crystal but isnot straight. A pore contains section where the direction of the porechanges, generally multiple times, but still connects two sides of thecrystal. A cavity is a polyhedral pore, which has at least one facedefined by a ring large enough to be penetrated by compounds having asize that is less than the size of the ring, but which is not infinitelyextended (i.e. not a channel). A channel is a pore that is infinitelyextended in one dimension and is large enough to allow guest species todiffuse along its length. Channels can intersect to form 2- or3-dimensional channel systems. The windows have molecular size and canadsorb chemical species small enough to pass through them. One factorthat controls the ability to adsorb molecules into the zeolite is thesize of the window or opening of the pore. A cage is a polyhedral porewhose windows are too narrow to be penetrated by guest species largerthan H₂O. This mean that the window of a cage has a maximum size of a6-member ring.

The term “framework” means a corner-sharing network of tetrahedrallycoordinated atoms. The term “structure” means both the framework andextra-framework constituents.

There are three different volumes associated with a framework: the totalvolume of the framework, the volume of the channels and the volume ofthe cavities.

The term “extra-framework” refers to a material, preferably a metal,that is not located within the framework of a molecular sieve. The term“extra-framework metal” refers to a metal located on extra-frameworksite. The metal is from one of the groups VB, VIIB, VIIB, VIIIB, IB, orIIB of the Periodic Table and has been deposited onto extra-frameworksites on the external surface or within the channels, cavities, or cagesof the molecular sieves. Metals may be in one of several forms,including, but not limited to, zerovalent metal atoms or clusters,isolated cations, mononuclear or polynuclear oxycations, or as extendedmetal oxides.

The new intergrowth zeolites herein described are related to the ABC-6family of structures, in particular those containing only doublesix-rings (D6Rs)(http://europe.iza-structure.org/IZA-SC/intergrowth_families/ABC_6.pdf).The ABC-6 structures are built up from 6Rs with different stackingarrangements along one axis and linked by 4Rs. The 6R units can becentred on three different positions along the hexagonal ab-plane: A (0,0, 0), B (2/3, 1/3, 0) and C (1/3, 2/3, 0).

The molecular sieves described herein comprise intergrowths having acha-aft-“sfw-GME tail”.

An activated molecular sieve refers to a molecular sieve comprising anintergrowth having a cha-aft-“sfw-GME tail, as described herein, wherethere are no structure directing agents in the molecular sieve.

Intergrown molecular sieve phases are disordered planar intergrowths ofmolecular sieve frameworks. Reference is directed to the “Catalog ofDisordered Zeolite Structures,” 2000 Edition, published by the StructureCommission of the International Zeolite Association and to the“Collection of Simulated XRD Powder Patterns for Zeolites,” FifthRevised Edition, Elsevier, 2007, published on behalf of the StructureCommission of the International Zeolite Association for a detailedexplanation on intergrown molecular sieve phases.

In a first aspect of the invention, provided are molecular sieves havingintergrowths comprising a cha-aft-“sfw-GME tail” and one or morestructure directing agents. These molecular sieves can be described asbeing “as-made”. All 6-rings are present as double 6-rings in thesemolecular sieves. The use of italics indicates that the gme cavity (gme)associated with each aft cavity (aft) and the 2 gme cavities associatedwith each sfw cavity (sfw) are included. Cavities of cha and aft arereferenced in lower case to include local AFX and AFT regions in theintergrowths. The term “sfw-GME” covers all cavities, includingassociated gme cavities, of the size of sfw and larger. Intergrowths ofCHA-GME are described in the literature, however this does not mean thatthere is a GME phase present, but rather a range of cavity sizes up tothe size of the particle of the molecular sieve. These molecular sievescontaining this intergrowth is referred to herein as JMZ-11A, JMZ-11B,JMZ-11C and JMZ-11D.

The molecular sieve can be an aluminosilicate or a metal-substitutedaluminosilicate, preferably an aluminosilicate. When the molecular sieveis an aluminosilicate, it can have a silica to alumina ratio (SAR) of 20or less, preferably 15 or less, more preferably 10 or less.

The molecular sieve can comprise phosphorus in the framework, and can bean aluminophosphate (AlPO), a metal-substituted aluminophosphate(MeAlPO), a silico-aluminophosphate (SAPO), or a metal substitutedsilico-aluminophosphate,

The molecular sieve can comprise one or more SDAs. The first SDA(SDA-1), which is required, can be anN,N-dimethyl-3,5-dimethylpiperidinium cation or anN,N-diethyl-2,6-dimethylpiperidinium cation. The second SDA (SDA-2),which can be present, is a CHA generating SDA, such as such as atrimethyladmandylammonium cation, a tetraethylammonium cation, atrimethylbenzylammonium cation, a trimethylcyclohexylammonium cation ora trimethyl(cyclohexylmethyl)ammonium or a phenyltrimethylammoniumcation. The third SDA (SDA-3), which can be present, is a AFX generatingSDA, such as a 1,3-bis(1-adamantyl)imidazolium,1,1-(butane-1,4-diyl)bis-(quinuclidin-1-ium),1,1-(pentane-1,5-diyl)bis-(quinuclidin-1-ium),1,1′-(1,4-butanediyl)bis(4-aza-1-azoniabicyclo[2.2.2]octane),1,1′-(1,5-pentanediyl)bis(4-aza-1-azoniabicyclo[2.2.2]octane). Theamount of SDA-2 and or SDA-3 cations used can change the proportion ofthe cha-aft-“sfw-GME tail”.

A molecular sieve of the first aspect of the invention can comprise atleast one metal within the framework where the metal is selected from atleast one of the metals of Groups IIIA, IB, IIB, VA, VIA, VIIA, VIIIA ofthe Periodic Table, and combinations thereof. Preferably the metal isone or more of cerium, chromium, cobalt, copper, iron, magnesium,manganese, molybdenum, nickel, palladium, platinum, rhodium, titanium,tungsten, vanadium and zinc. More preferably the metal is one or more ofcobalt, copper, iron, manganese and zinc.

XRD Analysis

One of the characteristics of molecular sieves is their XRD pattern. TheXRD pattern of SDA containing molecular sieves of the first aspect ofthe invention and activated molecular sieves of the second aspect of theinvention were obtained using a Bruker D8 Advance fitted with a copperanode (x-ray wavelength 1.5406 A) and a LynxEye detector. The primarybeam was fitted with a Goebels mirror and had a measurement circle of280 mm, a slit of 0.22 mm and an axial soller of 2.5°. The secondarybeam also had a measurement circle of 280 mm and axial soller of 2.5°.No slit was present. Step scanned data were collected between 3 and 100°two-theta with a step size of 0.022 at 1.5 steps/second. The sample wasrotated at 15 rpm. The collected data were analysed with DIFFRAC.SUITEEVA Bruker software.

The relative intensities, 100×I/I₀, where I₀ is the intensity of thestrongest line or peak, and d, the interplanar spacing in Angstromscorresponding to the recorded lines, were calculated. Minor variationsin the diffraction patterns of an SDA containing intergrowth and anactivated molecular sieve in the tables or figures can also result fromvariations in the organic compound used in the preparation, the presenceof water in the sample and from variations in the Si and Al mole ratiosfrom sample to sample. Notwithstanding these minor perturbations, thebasic crystal structures for the SDA containing intergrowth remainsubstantially unchanged. Similar variations can also be found in theX-ray diffraction patterns of activated molecular sieve samples.

As will be understood by those of skill in the art, the determination ofthe parameter 2θ is subject to both human and mechanical error, which incombination can impose an uncertainty of about ±0.2° on each reportedvalue of 20. This uncertainty is, of course, also manifested in thereported values of the d-spacings, which are calculated from the 2θ.values. This imprecision is general throughout the art and is notsufficient to preclude the differentiation of the present crystallinematerials from each other and from the compositions of the prior art. Insome of the x-ray patterns reported, the relative intensities of thed-spacings are indicated by the notations vs, s, m, and w whichrepresent very strong, strong, medium, and weak, respectively. In termsof relative intensity (100×I/I₀), the above designations are defined as:w (weak)<20; m (medium) is ≥20 and <40; s (strong) is ≥40 and <60; andvs (very strong) is ≥60. When the intensity is near the endpoint for arange, the intensity may be characterized was being in either of theranges. For example, intensities of 18-22 may be listed as w-m. However,due to variations in intensity of the lines, as known in the art, one ormore of the lines may have an intensity that is in an adjacent range.

In a second aspect of the invention, JMZ-11 and the four subgroups ofthe JMZ-11 family of molecular sieves, JMZ-11A, JMZ-11B, JMZ-11C andJMZ-11D, described herein, are present in an activated form. The term“activated” refers to a molecular sieve that has had two or morestructure directing agents (SDAs) removed from the framework structureor to one or more processes that can remove a structure directing agentfrom a molecular sieve. A material containing two or more SDAs canbecome activated by a number of process known to one skilled in the art,such a calcination or treatment with peroxide.

The term “calcine”, or “calcination”, means heating the material in air,oxygen or an oxygen containing gas atmosphere. This definition isconsistent with the IUPAC definition of calcination. (IUPAC. Compendiumof Chemical Terminology, 2nd ed. (the “Gold Book”). Compiled by A. D.McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford(1997). XML on-line corrected version: http://goldbook.iupac.org (2006-)created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins.ISBN 0-9678550-9-8. doi:10.1351/goldbook.) Calcination is performed todecompose a metal salt and promote the exchange of metal ions within thecatalyst and also to adhere the catalyst to a substrate. Thetemperatures used in calcination depend upon the components in thematerial to be calcined and generally are between about 400° C. to about900° C. for approximately 1 to 24 hours. In some cases, calcination canbe performed up to a temperature of about 1200° C. In applicationsinvolving the processes described herein, calcinations are generallyperformed at temperatures from about 400° C. to about 700° C. forapproximately 1 to 8 hours, preferably at temperatures from about 400°C. to about 650° C. for approximately 1 to 4 hours.

In addition to removal of the structure directing agent, it is preferredthat any alkaline or alkaline earth cations present be removed.Preferably, alkaline or alkaline earth cations can be removed withtreatment with an acid or ammonia solution. This ion-exchange can beperformed on an SDA containing intergrowth or a structure directingagent free intergrowth. The crystallinity of the material is betterpreserved when the alkaline or alkaline earth cations are removed in theSDA containing form.

One or more activated molecular sieves can be useful as a catalyst incertain applications. Activated intergrowth crystals are preferablycalcined, but can also be used without calcination once the SDAs areremoved. An activated molecular sieve can be used either without apost-synthesis metal exchange or with a post-synthesis metal exchange,preferably with a post-synthesis metal exchange. Thus, in certainaspects of the invention, provided is a catalyst comprising an activatedmolecular sieve that is free, or essentially free, of any exchangedmetal, particularly post-synthesis exchanged or impregnated metals. Theterm “essentially free” of exchanged metals means that the metals arepresent at <0.1 wt. %. Activated intergrowths preferably comprise one ormore catalytic metal ions exchanged or otherwise impregnated into thechannels and/or cavities of the molecular sieve. Examples of metals thatcan be post-zeolite synthesis exchanged or impregnated includetransition metals, including copper, nickel, zinc, iron, tungsten,molybdenum, cobalt, titanium, zirconium, manganese, chromium, vanadium,niobium, tin, bismuth, antimony, noble metals including platinum groupmetals (PGMs), such as ruthenium, rhodium, palladium, indium, platinum,and precious metals such as gold and silver; alkaline earth metals suchas beryllium, magnesium, calcium, strontium, and barium; and rare earthmetals such as lanthanum, cerium, praseodymium, neodymium, europium,terbium, erbium, ytterbium, and yttrium. Preferred transition metals forpost-synthesis exchange are base metals, and preferred base metalsinclude those selected from the group consisting of manganese, iron,cobalt, nickel, copper, noble metals including platinum group metals(PGMs) and mixtures thereof.

The transition metal can be present in an amount of about 0.1 to about10 weight percent, for example about 0.1 to about 5 weigh percent, about0.1 to about 1.0 weight percent, about 2.5 to about 3.5 weight percent,and about 4.5 to about 5.5 weight percent, wherein the weight percent isrelative to the total weight of the molecular sieve material, and theendpoints can be included.

Particularly preferred exchanged metals include copper and iron,particularly when combined with calcium and/or cerium and particularlywhen the transition metals (T_(M)) and the alkaline metals (A_(M)) arepresent in a T_(M):A_(M) molar ratio of about 15:1 to about 1:1, forexample about 10:1 to about 2:1, about 10:1 to about 3:1, or about 6:1to about 4:1, where the endpoints can be included

Metals incorporated post-synthesis can be added to the molecular sievevia any known technique such as ion exchange, impregnation, isomorphoussubstitution, etc.

These exchanged metal cations are distinct from metals constituting themolecular framework of the molecular sieve, and thus metal exchangedmolecular sieves are distinct from metal-substituted molecular sieves.

JMZ-11A

The XRD pattern of SDA containing JMZ-11A was determined from a sampleof Example 1. The X-ray diffraction pattern is shown in FIG. 1 and thepeak values are summarized in Table 1. FIG. 1 shows the intensitiesnormalized to a maximum peak height of 100%. This pattern and the peakvalues are characteristic of species of SDA containing JMZ-11.

When the molecular sieve is an aluminosilicate and the structuredirecting agent comprises a N,N-dimethyl-3,5-dimethylpiperidiniumcation, a powder XRD pattern of hydrated aluminosilicate JMZ-11A canhave the characteristic lines with the corresponding intensities asshown in Table 1.

TABLE 1 2-Theta [°] ^((a)) d-spacing [Å] Rel. Int. [%] ^((b)) 7.7 11.47vs 9.6 9.17 w 11.8 7.51 m 13.1 6.74 s 15.2 5.84 m 17.6 5.04 m 18.0 4.92vs 20.0 4.44 s 21.0 4.23 w 21.9 4.06 vs 22.6 3.93 w 26.2 3.40 s 27.33.27 w 28.1 3.18 m 28.7 3.11 w 30.3 2.95 s 31.0 2.89 m 31.6 2.83 m 33.72.66 w 34.8 2.58 m 43.7 2.07 w 48.0 1.89 w ^((a)) = ±0.2; ^((b)) Peakswith Rel. Int. <5% are not listed

The term “Rel. Int.” (Relative Intensity” refers to designations basedon the relative intensity (100×I/I₀), where the labels are defined as: w(weak)<20; m (medium) is ≥20 and <40; s (strong) is ≥40 and <60; and vs(very strong) is ≥60.

In a second aspect of the invention, JMZ-11A is present in an activatedform. The XRD pattern of activated JMZ-11A was determined from a sampleof Example 1. The X-ray diffraction pattern is shown in FIG. 2 and thepeak values are summarized in Table 2. FIG. 2 shows intensitiesnormalized to a maximum peak height of 100%. This pattern and the peakvalues are characteristic of species of activated JMZ-11.

TABLE 2 2θ [°] ^((a)) d-spacing [Å] Rel. Int. [%] ^((b)) 7.7 11.49 m 9.69.20 w 11.7 7.53 m 13.1 6.74 vs 15.2 5.84 w 17.6 5.03 w 18.1 4.91 s 20.04.43 m 20.8 4.26 w 21.9 4.05 m 22.7 3.92 w 26.2 3.39 m 27.4 3.25 w 28.13.17 w 28.7 3.11 w 30.4 2.94 m 31.0 2.88 w 31.6 2.83 w 33.8 2.65 w 34.92.57 w 43.9 2.06 w 48.1 1.89 w ^((a)) = ±0.2; ^((b)) Peaks with Rel.Int. <5% are not listed

JMZ-11B

The XRD pattern of SDA containing JMZ-11B was determined from a sampleof Example 2. The X-ray diffraction pattern is shown in FIG. 3 and thepeak values are summarized in Table 3. FIG. 3 shows the intensitiesnormalized to a maximum peak height of 100%. This pattern and the peakvalues are characteristic of species of SDA containing JMZ-11B.

When the molecular sieve is an aluminosilicate and the structuredirecting agent comprises a N,N-diethyl-2,6-dimethylpiperidinium cation,a powder XRD pattern of hydrated aluminosilicate JMZ-11B can have thecharacteristic lines with the corresponding intensities as shown inTable 3.

TABLE 3 2-Theta [°] ^((a)) d-spacing [Å] Rel. Int. [%] 7.5 11.71 m-s10.5 8.43 w 12.9 6.84 s-vs 15.0 5.90 w 17.8 4.98 vs 19.8 4.47 m 21.34.17 m 21.9 4.05 w-m 22.5 3.96 w-m 26.0 3.42 s-vs 27.1 3.28 w 28.0 3.18w 30.2 2.96 m-s 31.0 2.88 m 31.6 2.83 w 34.6 2.59 m 43.5 2.08 w-m 47.81.90 w ^((a)) = ±0.2; ^((b)) Peaks with Rel. Int. <5% are not listed

In a second aspect of the invent, JMZ-11B is present in an activatedform. The XRD pattern of activated JMZ-11B was determined from a sampleof Example 2. The X-ray diffraction pattern is shown in FIG. 4 and thepeak values are summarized in Table 4. FIG. 4 shows the intensitiesnormalized to a maximum peak height of 100%. This pattern and the peakvalues are characteristic of species of activated JMZ-11B.

TABLE 4 2-Theta [°] ^((a)) d-spacing [Å] Rel. Int. [%] ^((b)) 7.6 11.65w-m 10.8 8.22 w 13.0 6.80 vs 15.1 5.88 w 17.9 4.94 s 19.9 4.45 w-m 21.44.15 w-m 22.1 4.02 w 22.5 3.94 w 26.1 3.41 m 27.2 3.27 w 28.1 3.17 w30.3 2.95 w-m 31.1 2.87 w 31.8 2.81 w 34.7 2.58 w 43.7 2.07 w 48.0 1.90w ^((a)) = ±0.2; ^((b)) Peaks with Rel. Int. <5% are not listed

JMZ-11C

The XRD pattern of SDA containing JMZ-11C was determined from a sampleof Example 3. The X-ray diffraction pattern is shown in FIG. 5 and thepeak values are summarized in Table 5. FIG. 5 shows the intensitiesnormalized to a maximum peak height of 100%. This pattern and the peakvalues are characteristic of species of SDA containing JMZ-11C.

When the molecular sieve is an aluminosilicate and the structuredirecting agent comprises N,N-dimethyl-3,5-dimethylpiperidinium cationsand 1,3-bis(1-adamantyl) imidazolium cations, a powder XRD pattern ofhydrated aluminosilicate JMZ-11C can have the characteristic lines withthe corresponding intensities as shown in Table 5.

TABLE 5 2-Theta [°] ^((a)) d-spacing [Å] Rel. Int. [%] ^((b)) 7.5 11.86w 8.1 10.92 w 9.2 9.61 w 11.6 7.62 m 12.9 6.85 vs 17.4 5.08 w 17.9 4.95s 19.8 4.47 w 20.5 4.32 w 21.8 4.08 m 22.2 4.01 w 26.0 3.42 m 28.1 3.18w 30.2 2.95 w 30.6 2.92 w 31.5 2.84 w 31.8 2.81 w 34.7 2.58 w ^((a)) = ±0.2; ^((b)) Peaks with Rel. Int. < 5% are not listed

In a second aspect of the invent, JMZ-11C is present in an activatedform. The XRD pattern of activated JMZ-11C was determined from a sampleof Example 3. The X-ray diffraction pattern is shown in FIG. 6 and thepeak values are summarized in Table 6. FIG. 6 shows the intensitiesnormalized to a maximum peak height of 100%. This pattern and the peakvalues are characteristic of species of activated JMZ-11C.

TABLE 6 2-Theta [°] ^((a)) d-spacing [Å] Rel. Int. [%] ^((b)) 7.5 11.75m 8.0 11.03 w 9.4 9.41 w 11.5 7.68 w-m 12.9 6.86 s 15.0 5.91 w-m 15.95.57 w 17.4 5.11 m 17.7 5.00 vs 19.8 4.48 s 20.6 4.32 m-s 21.7 4.09 vs22.5 3.96 w-m 26.0 3.41 m 27.2 3.27 w 27.8 3.21 m 28.5 3.13 w 30.2 2.96s 30.6 2.92 s 31.4 2.85 m-s 33.5 2.68 w 34.6 2.59 m 42.8 2.11 w 43.62.08 w-m ^((a)) = ±0.2; ^((b)) Peaks with Rel. Int. <5% are not listed

JMZ-11D

The XRD pattern of SDA containing JMZ-11D was determined from a sampleof Example 4. The X-ray diffraction pattern is shown in FIG. 7 and thepeak values are summarized in Table 7. FIG. 7 shows the intensitiesnormalized to a maximum peak height of 100%. This pattern and the peakvalues are characteristic of species of SDA containing JMZ-11B.

When the molecular sieve is an aluminosilicate and the structuredirecting agent comprises a N,N-dimethyl-3,5-dimethylpiperidinium andtrimethyladmandylammonium cations, a powder XRD pattern of hydratedaluminosilicate JMZ-11D can have the characteristic lines with thecorresponding intensities as shown in Table 7.

TABLE 7 2-Theta [°] ^((a)) d-spacing [Å] Rel. Int. [%] ^((b)) 7.6 11.66m 9.7 9.1 w 11.6 7.59 m 13 6.79 vs 15.1 5.88 w 17.5 5.06 w 17.9 4.95 s19.9 4.45 m 20.8 4.26 w 21.8 4.07 m 22.6 3.93 w 26.1 3.41 m 28 3.19 w30.3 2.95 w-m 30.9 2.89 w 31.6 2.83 w 34.8 2.58 w ^((a)) = ±0.2; ^((b))Peaks with Rel. Int. <5% are not listed

In a second aspect of the invent, JMZ-11D is present in an activatedform. The XRD pattern of activated JMZ-11D was determined from a sampleof Example 4. The X-ray diffraction pattern is shown in FIG. 8 and thepeak values are summarized in Table 8. FIG. 8 shows the intensitiesnormalized to a maximum peak height of 100%. This pattern and the peakvalues are characteristic of species of activated JMZ-11D.

TABLE 8 2-Theta [°] ^((a)) d-spacing [Å] Rel. Int. [%] ^((b)) 7.6 11.66m 9.7 9.10 w 11.6 7.59 m 13.0 6.79 vs 15.1 5.88 w 17.5 5.06 w 17.9 4.95s 19.9 4.45 m 20.8 4.26 w 21.8 4.07 m 22.2 4.00 w 26.1 3.40 m 28.0 3.19w 30.3 2.95 w-m 30.9 2.89 w 31.6 2.83 w 31.8 2.80 w 34.8 2.58 w ^((a)) =±0.2; ^((b)) Peaks with Rel. Int. <5% are not listed

Methods of Analyzing Intergrowth

The molecular sieves described herein represent a family of molecularsieves comprising intergrowths of cha and aft having an “sfw-GME tail”.This will be defined fully below but these differ from stochasticintergrowths of CHA and GME such as babelite. They also differ fromstochastic intergrowths of CHA and AFX or CHA and AFT which have nocavities larger that aft. The intergrowths described herein belong tothe ABC-6 family of zeolites, specifically only those with a stackingsequence consisting of only double-6 rings (D6R).

The intergrowth can form different structures within the bulk molecularsieve. This can result in the appearance of a separate phase recognizedby XRD. The relative proportions of each of the intergrowth phases canbe analyzed by x-ray diffraction and, in particular, by comparing theobserved patterns with calculated patterns generated using algorithms tosimulate the effects of stacking disorder.

DIFFaX is a fortran computer program based on a mathematical model forcalculating intensities from crystals containing planar faults (Treacy,M. M. J.; Newsam, J. M.; Deem, M. W.: A general recursion method forcalculating diffracted intensities from crystals containing planarfaults. Proc. R. Soc. London Ser. A 433 (1991) 499-520).

DIFFaX is the simulation program selected by, and available from, theInternational Zeolite Association to simulate the powder XRD patternsfor randomly intergrown phases (see “Collection of Simulated XRD PowderPatterns for Zeolites,” Fifth Revised Edition, Elsevier, 2007, publishedon behalf of the Structure Commission of the International ZeoliteAssociation). DIFFaX has been used to theoretically study zeolite beta(Treacy et al 1991), AEI-CHA intergrowths in numerous patents and manyother intergrowths in zeolites and other materials.

Pure CHA has a 3-dimensional pore system with cha cavities linked by8-rings windows forming 8-ring channels. (FIG. 10 )

Pure GME has a 3-dimensional pore system with gme cavities linked by8-rings to 12-ring channels that runs through the entire length of acrystallite in the c-axis direction. (FIG. 11 )

Intergrowths of CHA and GME are well known. In a CHA-GME intergrowth,the CHA units block off the ends of the 12-ring channels and theresulting GME units can have cavities from as small as aft to almost thecrystal length in the direction of the c-axis (as well as associated gmecavities). The cavities in this system can be described using an integerthat is proportional to its length in the c-direction: 1=gme, 2=cha,3=aft, 4=sfw, 5=“5”, 6=“6”, etc. Hereafter, the gme cavities are ignoredas they are implicitly present in respect to the larger cavities (1 peraft, 2 per sfw, 3 per “5”, etc or (n−2) per “n” cavity for n>2). The gmecavities provide the framework that links the aft and larger cavities toone another in the basal plane directions. CHA units have cavities ofsize 2 and what is called GME in the intergrowth has cavity sizes thatcan range from 3 to “infinity” depending on how soon another faultcloses off the 12-ring channel.

The stochastic intergrowth model for DIFFaX input is shown in FIG. 12has individual layers 5 Angstrom thick, as enumerated in the CHA-GMEfile in the Examples folder on Mike Treacy's DIFFaX website.(http://www.public.asu.edu/%7Emtreacy/DIFFaX.html). The basis of eachlayer is the top 6-ring of a double 6-ring linked to the bottom 6-ringof an adjacent double 6-ring. The forward slash and backslash lines inthe schematic of the stacking in FIG. 13 represent the direction of thislinkage. The 6-rings are omitted for simplicity. Forward slash indicatesAB, BC or CA stacking whilst backslash indicates AC, CB or BA stackingin theses ABC double 6-ring materials.

CHA-GME intergrowths that have been described in the literature haveessentially a stochastic intergrowth wherein one fault probability, p,describes the distribution of cavity sizes in the material. Analysis ofthis model leads to a monotonically decreasing fractional population, f,of cavities with size, n; one in whichf _(n+1) =pf _(n)for n≥2and f ₂=(1−p).

An example of this is given by Babelite which has p=0.5. (R. Szostak, K.P. Lillerud, J. Chem. Soc., Chem. Commun. 1994, 2357). The range ofdistributions as a function of p is shown in FIG. 14 .

In stochastic intergrowths, only the identity of the current layerdetermines the stacking probability of the next layer; there is nomemory effect of the previous layer. The Treacy et al paper includes thememory or Reichweite concept to describe clustering of faults (or blockintergrowths) by including the influence of the previous layer on thestacking probability of the next (known as Reichweite 1). This is alsoshown in FIG. 13 . For example, if p is small large blocks of CHA wouldalternate with GME like large cavities.

The extension to Reichweite n wherein the current layer and previous nlayers influence the next layer is straightforward and has beendescribed by H. Jagodzinski, Acta Cryst. 2 208-14 (1949). The essentialfeatures of the intergrowths in this application can be described by aReichweite 2 DIFFaX model (FIG. 15 ). In the case of Reichweite 2, thestacking probability of a new layer in the crystallographic c-axisdepends on the stacking of the previous 2 layers. The forward-slashesand back-slashes in parenthesis in FIG. 15 indicate the stacking of the2 previous layers. Layer type 1 followed by Layer 1 is a CHA stackingsequence and Layer 3 followed by Layer 6 is part of a GME sequence.Although this model considers only the framework directly and not thestructure directing agent molecules, it nevertheless is a reasonabledescriptor.

This is because the Reichweite 2 DIFFaX model explicitly generates cha,aft and sfw cavities with the associated gme cavities for aft and sfw.All of the known, ordered ABC-6, double 6-ring frameworks are includedin the description—CHA, AFT, AFX and SFW. The stacking probabilities p,q, r, and s are defined in the 8×8 matrix below and all have values inthe range 0 to 1. The entries in the row, m, of the matrix are theprobabilities that Layer m will be followed by Layer in column n. Thesequence of Layers and the corresponding values of the stackingprobabilities p, q, r, s for the known ordered phases are listed.

In the general case it is straightforward to calculate from the stackingprobabilities the distribution of cavity sizes, f_(n), ignoring the gmecavities as they are in strict relation to the larger cavities. (FIG. 16)

If r=1, there are no cavities larger than sfw. If s=0 there are no sfwcavities and there is no “sfw-GME” tail. So, if r=1 and s=0, there iseither a stochastic CHA-AFX intergrowth if q=(1−p) or a stochasticCHA-AFT intergrowth if q=1. But, in terms of the model, q need not be soconstrained. Hence the concept of cha-aft intergrowths containing localregions of CHA, AFT and AFX.

If s>0 there is an “sfw-GME” tail such that:f _(n+1) =pf _(n) but only for n>=4similar to the distribution for stochastic CHA-GME but with sfw ratherthan cha as the smallest cavity (ignoring the associated gme cavities).The probability r controls the length of the tail, that is how quicklythe distribution drops off with increasing cavity size. As r approacheszero the “sfw-GME” tail extends to larger cavities. The number fractionof cha cavities is q/(p+q), of aft cavities is p(1−s)/(p+q) and ofcavities in the “sfw-GME” tail ps/(p+q). Note these fractions areindependent of the probability r that controls the length of the tail.But the diffraction pattern is dependent on these and r.

However, if s=(1−r)=p and q=(1−p), these equations reduce tof_(n+1)=pf_(n) for n>=2, with f₂=(1−p). In this situation there is nomemory effect (Reichweite 0) and this results in a stochastic CHA-GMEintergrowth (FIG. 17 ) in which the stacking probability of a layer isindependent of the previous stacking. The larger the value of p, thesmaller the percentage of cha cavities and the larger the averagenon-gme cavity size as demonstrated in FIG. 17 . Note that if gmecavities are included the average cavity size for all ABC-6 d6Rmaterials (ordered or disordered) is precisely 2.

JMZ-11A, JMZ-11B, JMZ-11C and JMZ-11D are not stochastic intergrowths ofCHA-GME. They are best described as cha-aft-“sfw-GME” intergrowths,which can be described by the Reichweite 2 model. The three materialscomprise a monotonically decreasing sfw-GME tail encompassing the rangefrom sfw cages to “infinity”, while the cha and aft cages are in verydifferent proportions relative to this tail than those in stochasticCHA-GME intergrowths. The cage distributions within JMZ-11A, JMZ-11B,JMZ-11C and JMZ-11D as determined by the above analysis are shown inFIG. 18 to 21 , respectively.

The use of lower case cha and aft here is to include local AFX and AFTregions in the intergrowths. Stochastic CHA-AFX intergrowths willinevitably have local regions of AFT; with more AFT than AFX when theprobability of CHA faulting is small. However, a CHA-AFT stochasticintergrowth would have no local AFX regions, and simulated x-raydiffraction (using DIFFaX) patterns are different. Stochastic CHA-AFXand CHA-AFT intergrowths are subsets of more general cha-aftintergrowths.

The “sfw-GME” tail is a significant fraction of the volume in thesecha-aft-“sfw-GME” intergrowths that cannot be ignored. CHA-AFT andCHA-AFX (or more generally cha-aft) intergrowths do not have such atail—there are no cavities larger than aft. The X-ray diffractionpatterns of these cha-aft-“sfw-GME” materials cannot be approximatedwithout the “sfw-GME” tail. Annular dark-field images recorded byaberration-corrected Scanning Transmission Electron Microscopy confirmsthis model.

FIGS. 22-25 show comparisons between the experimental XRD patterns ofactivated JMZ-11A, JMZ-11B, JMZ-11C, and JMZ-11D and the DIFFaXsimulations carried out using the Reichweite 2 description. This figuresshow that the DIFFaX simulations carried out using the Reichweite 2description provide a good description of the composition of theintergrowths.

In powder XRD patterns from stochastic CHA-GME intergrowths the peak at9.5 degrees broadens but does not shift. In the JMZ-11 family, whichcomprises JMZ-11A, JMZ-11B, JMZ-11C and JMZ-11D, this peak shiftsubstantially from 9.5 degrees but the broadening of it and the raisedbackground between 7.7 and 13.1 degrees are much greater than instochastic CHA-GME intergrowths (FIG. 9 ). The sfw-GME tail must beincluded to simulate this correctly for dehydrated, activated samples.

JMZ-11A comprises a structure direct agent (SDA-1), where SDA-1 is aN,N-dimethyl-3,5-dimethylpiperidinium cation, cha cavities, aft cavitiesand an “sfw-GME” tail, wherein the cha cavities are present at about 45to about 65%, preferably about 54%, of the cavities in the tail, the aftcavities are present at about 18 to about 28%, preferably about 23% ofthe cavities in the tail, and the remaining about 7 to about 37%,preferable about 23%, of larger cavities in the “sfw-GME” tail. The gmecavities associated with the aft and larger cavities are not included inthese figures. The “sfw-GME” tail accounts for about 35-80% of thevolume of the molecular sieve or the molecular sieve particle,preferably about 68%. JMZ-11A has a monotonically decreasingdistribution of cavity sizes, but it cannot be described as a stochasticCHA-GME intergrowth.

JMZ-11B comprises a structure direct agent (SDA-1), where SDA-1 is aN,N-diethyl-2,6-dimethylpiperidinium cation, cha cavities, aft cavitiesand an “sfw-GME” tail, wherein the cha cavities are present at about 55to about 75%, preferably about 65%, of the cavities in the tail, the aftcavities are present at about 0 to about 10%, preferably about 5% of thecavities in the tail, and the remaining about 15 to about 45%,preferable about 30%, of larger cavities in the “sfw-GME” tail. The gmecavities associated with the aft and larger cavities are not included inthese figures. The “sfw-GME” tail accounts for about 40-80% of thevolume of the molecular sieve or the molecular sieve particle,preferably about 64%. JMZ-11B has a monotonically decreasingdistribution of cavity sizes, but it cannot be described as a stochasticCHA-GME intergrowth.

JMZ-11C comprises two structure direct agents, anN,N-dimethyl-3,5-dimethylpiperidinium cation and a1,3-bis(1-adamantyl)imidazolium cation, cha cavities, aft cavities andan “sfw-GME” tail, wherein the cha cavities are present at about 30 toabout 45%, preferably about 39%, of the cavities in the tail, the aftcavities are present at about 45 to about 65%, preferably about 54% ofthe cavities in the tail, and the remaining about 2 to about 20%,preferable about 7%, of larger cavities in the “sfw-GME” tail. The gmecavities associated with the aft and larger cavities are not included inthese figures. The “sfw-GME” tail accounts for about 5-45% of the volumeof the molecular sieve or the molecular sieve particle, preferably about23%. JMZ-11C has a monotonically decreasing distribution of cavitysizes, but it cannot be described as a stochastic CHA-GME intergrowth.

JMZ-11D comprises two structure direct agents, anN,N-dimethyl-3,5-dimethylpiperidinium cation and atrimethyladmandylammonium cation, cha cavities, aft cavities and an“sfw-GME” tail, wherein the cha cavities are present at about 55 toabout 75%, preferably about 65%, of the cavities in the tail, the aftcavities are present at about 7 to about 17%, preferably about 12% ofthe cavities in the tail, and the remaining about 8 to about 38%,preferable about 23%, of larger cavities in the “sfw-GME” tail. The gmecavities associated with the aft and larger cavities are not included inthese figures. The “sfw-GME” tail accounts for about 50-90% of thevolume of the molecular sieve or the molecular sieve particle,preferably about 75%. JMZ-11D has a monotonically decreasingdistribution of cavity sizes, but it cannot be described as a stochasticCHA-GME intergrowth.

In a third aspect of the invention, a catalyst comprises an activatedH-form of one or more molecular sieves of the second aspect of theinvention, described herein, and can further comprise at least oneextra-framework metal selected from the group consisting of Ag, Au, Ce,Co, Cr, Cu, Fe, Ga, In, Ir, Mn, Mo, Ni, Os, Pd, Pt, Re, Rh, Ru, Sn andZn, preferably Cu, Fe, Co and Ni, more preferably Cu and Fe, mostpreferably Cu.

The activated H-form of the intergrowth in the catalyst can compriseabout 0.1 to about 5 weight percent of at least one extra-frameworkmetal.

In a fourth aspect of the invention, a catalyst article for treatingexhaust gas comprises a catalyst comprising an activated H-form of amolecular sieve of the second aspect of the invention and can furthercomprise at least one extra-framework metal selected from the groupconsisting of Ag, Au, Ce, Co, Cr, Cu, Fe, Ga, In, Ir, Mn, Mo, Ni, Os,Pd, Pt, Re, Rh, Ru, Sn and Zn, preferably Co, Cu, Fe, and Ni, morepreferably Cu and Fe, most preferably Cu.

The activated H-form of a molecular sieve in the catalyst can compriseabout 0.1 to about 5 weight percent of at least one extra-frameworkmetal.

The catalyst can be disposed on and/or within a porous substrate,preferably a flow through or wall-flow filter.

Catalysts of the present invention are particularly applicable forheterogeneous catalytic reaction systems (i.e., solid catalyst incontact with a gas reactant). To improve contact surface area,mechanical stability, and/or fluid flow characteristics, the catalystscan be disposed on and/or within a substrate, preferably a poroussubstrate. A washcoat containing the catalyst can be applied to an inertsubstrate, such as corrugated metal plate or a honeycomb cordieritebrick. Alternatively, the catalyst is kneaded along with othercomponents such as fillers, binders, and reinforcing agents, into anextrudable paste which then can be extruded through a die to form ahoneycomb brick or extruded body such as a cylinder, trilobe orquadralobe. The catalyst may also be in the form of a micro-sphericalparticle (10-150 microns in diameter) containing an activated molecularsieve of the present invention together with fillers, binders and/orreinforcing agents. The micro-spherical particle can be prepared byspray drying or other suitable techniques. Accordingly, a catalystarticle can comprise an activated molecular sieve described hereincoated on and/or incorporated into a substrate.

The catalytic article can comprise a washcoat comprising an activatedmolecular sieve as described in the second aspect of the invention. Thewashcoat is preferably a solution, suspension, or slurry. Suitablecoatings include surface coatings, coatings that penetrate a portion ofthe substrate, coatings that permeate the substrate, or some combinationthereof.

A washcoat can also include non-catalytic components, such as fillers,binders, stabilizers, rheology modifiers, and other additives, includingone or more of alumina, silica, non-zeolite silica alumina, titania,zirconia, ceria. Where the catalyst is part of a washcoat composition,the washcoat can further comprise a binder containing Ce or ceria. Whenthe binder contains Ce or ceria, the Ce containing particles in thebinder are significantly larger than the Ce containing particles in thecatalyst. The catalyst composition can comprise pore-forming agents suchas graphite, cellulose, starch, polyacrylate, and polyethylene, and thelike. These additional components do not necessarily catalyze thedesired reaction, but instead improve the catalytic material'seffectiveness, for example, by increasing its operating temperaturerange, increasing contact surface area of the catalyst, increasingadherence of the catalyst to a substrate, etc. The washcoat loading on,or in, the substrate can be between about 0.3 g/in³ to about 3.5 g/in³,where the endpoints can be included. The loading can be a function ofthe type of substrate used and the backpressure that results from theloading on a specific type of substrate. The lower limit for thewashcoat loading can be 0.5 g/in³, 0.8 g/in³, 1.0 g/in³, 1.25 g/in³, or1.5 g/in³. The upper limit for the washcoat loading can be 3.5 g/in³,3.25 g/in³, 3.0 g/in³, 2.75 g/in³, 2.5 g/in³, 2.25 g/in³, 2.0 g/in³,1.75 g/in³ or 1.5 g/in³.

Two of the most common substrate designs to which catalyst can beapplied are plate and honeycomb. Preferred substrates, particularly formobile applications, include flow-through monoliths having a so-calledhoneycomb geometry that comprise multiple adjacent, parallel channelsthat are open on both ends and generally extend from the inlet face tothe outlet face of the substrate and result in a high-surfacearea-to-volume ratio. For certain applications, the honeycombflow-through monolith preferably has a high cell density, for exampleabout 600 to 800 cells per square inch, and/or an average internal wallthickness of about 0.18-0.35 mm, preferably about 0.20-0.25 mm. Forcertain other applications, the honeycomb flow-through monolithpreferably has a low cell density of about 150-600 cells per squareinch, more preferably about 200-400 cells per square inch. Preferably,the honeycomb monoliths are porous. In addition to cordierite, siliconcarbide, silicon nitride, ceramic, and metal, other materials that canbe used for the substrate include aluminum nitride, silicon nitride,aluminum titanate, α-alumina, mullite, e.g., acicular mullite,pollucite, a thermet such as Al₂OsZFe, Al₂O₃/Ni or B₄CZFe, or compositescomprising segments of any two or more thereof. Preferred materialsinclude cordierite, silicon carbide, and alumina titanate.

Plate-type catalysts have lower pressure drops and are less susceptibleto plugging and fouling than the honeycomb types, which is advantageousin high efficiency stationary applications, but plate configurations canbe much larger and more expensive. A honeycomb configuration istypically smaller than a plate type, which is an advantage in mobileapplications, but has higher pressure drops and plug more easily. Theplate substrate can be constructed of metal, preferably corrugatedmetal.

A catalyst article can be made by a process as herein described. Thecatalyst article can be produced by a process that includes the steps ofapplying preferably as a washcoat, of an activated molecular sieve,preferably an extra-framework metal containing activated molecularsieve, to a substrate as a layer either before or after at least oneadditional layer of another composition for treating exhaust gas hasbeen applied to the substrate. The one or more catalyst layers on thesubstrate, including the layer comprising an activated molecular sieve,are arranged in consecutive layers. As used herein, the term“consecutive” with respect to catalyst layers on a substrate means thateach layer is contact with its adjacent layer(s) and that the catalystlayers as a whole are arranged one on top of another on the substrate.

An activated molecular sieve catalyst can be disposed on the substrateas a first layer or zone and another composition, such as an oxidationcatalyst, reduction catalyst, scavenging component, or NO_(x) storagecomponent, can be disposed on the substrate as a second layer or zone.As used herein, the terms “first layer” and “second layer” are used todescribe the relative positions of catalyst layers in the catalystarticle with respect to the normal direction of exhaust gasflow-through, past, and/or over the catalyst article. Under normalexhaust gas flow conditions, exhaust gas contacts the first layer priorto contacting the second layer. The second layer can be applied to aninert substrate as a bottom layer and the first layer is a top layerthat is applied over the second layer as a consecutive series ofsub-layers.

The exhaust gas can penetrate (and hence contact) the first layer,before contacting the second layer, and subsequently returns through thefirst layer to exit the catalyst component.

The first layer can be a first zone disposed on an upstream portion ofthe substrate and the second layer is disposed on the substrate as asecond zone, wherein the second zone is downstream of the first.

The catalyst article can be produced by a process that includes thesteps of applying an activated molecular sieve, preferably as awashcoat, to a substrate as a first zone, and subsequently applying atleast one additional composition for treating an exhaust gas to thesubstrate as a second zone, wherein at least a portion of the first zoneis downstream of the second zone. Alternatively, a compositioncomprising an activated molecular sieve can be applied to the substratein a second zone that is downstream of a first zone containing theadditional composition. Examples of additional compositions includeoxidation catalysts, reduction catalysts, scavenging components (e.g.,for sulfur, water, etc.), or NO_(x) storage components.

To reduce the amount of space required for an exhaust system, individualexhaust components can be designed to perform more than one function.For example, applying an SCR catalyst to a wall-flow filter substrateinstead of a flow-through substrate serves to reduce the overall size ofan exhaust treatment system by allowing one substrate to serve twofunctions, namely catalytically reducing NO_(x) concentration in theexhaust gas and mechanically removing soot from the exhaust gas. Thesubstrate can be a honeycomb wall-flow filter or partial filter.Wall-flow filters are similar to flow-through honeycomb substrates inthat they contain a plurality of adjacent, parallel channels. However,the channels of flow-through honeycomb substrates are open at both ends,whereas the channels of wall-flow substrates have one end capped,wherein the capping occurs on opposite ends of adjacent channels in analternating pattern. Capping alternating ends of channels prevents thegas entering the inlet face of the substrate from flowing straightthrough the channel and existing. Instead, the exhaust gas enters thefront of the substrate and travels into about half of the channels whereit is forced through the channel walls prior to entering the second halfof the channels and exiting the back face of the substrate.

The substrate wall has a porosity and pore size that is gas permeable,but traps a major portion of the particulate matter, such as soot, fromthe gas as the gas passes through the wall. Preferred wall-flowsubstrates are high efficiency filters. Wall flow filters for use withthe present invention preferably have an efficiency of ≥70%, ≥about 75%,≥about 80%, or ≥about 90%. The efficiency can be from about 75 to about99%, about 75 to about 90%, about 80 to about 90%, or about 85 to about95%. Here, efficiency is relative to soot and other similarly sizedparticles and to particulate concentrations typically found inconventional diesel exhaust gas. For example, particulates in dieselexhaust can range in size from 0.05 microns to 2.5 microns. Thus, theefficiency can be based on this range or a sub-range, such as 0.1 to0.25 microns, 0.25 to 1.25 microns, or 1.25 to 2.5 microns.

Porosity is a measure of the percentage of void space in a poroussubstrate and is related to backpressure in an exhaust system:generally, the lower the porosity, the higher the backpressure.Preferably, the porous substrate has a porosity of about 30 to about80%, for example about 40 to about 75%, about 40 to about 65%, or fromabout 50 to about 60%, where the endpoints can be included.

The pore interconnectivity, measured as a percentage of the substrate'stotal void volume, is the degree to which pores, void, and/or channels,are joined to form continuous paths through a porous substrate, i.e.,from the inlet face to the outlet face. In contrast to poreinterconnectivity is the sum of closed pore volume and the volume ofpores that have a conduit to only one of the surfaces of the substrate.Preferably, the porous substrate has a pore interconnectivity volume of≥about 30%, more preferably ≥about 40%.

The mean pore size of the porous substrate is also important forfiltration. Mean pore size can be determined by any acceptable means,including by mercury porosimetry. The mean pore size of the poroussubstrate should be of a high enough value to promote low backpressure,while providing an adequate efficiency by either the substrate per se,by promotion of a soot cake layer on the surface of the substrate, orcombination of both. Preferred porous substrates have a mean pore sizeof about 10 to about 40 μm, for example about 20 to about 30 μm, about10 to about 25 μm, about 10 to about 20 m, about 20 to about 25 μm,about 10 to about 15 μm, and about 15 to about 20 μm.

In general, the production of an extruded solid body, such as honeycombflow-through or wall-flow filter, containing an activated molecularsieve, described herein, as a catalyst involves blending ab activatedmolecular sieve, a binder, an optional organic viscosity-enhancingcompound into an homogeneous paste which is then added to abinder/matrix component or a precursor thereof and optionally one ormore of stabilized ceria, and inorganic fibers. The blend is compactedin a mixing or kneading apparatus or an extruder. The mixtures haveorganic additives such as binders, pore formers, plasticizers,surfactants, lubricants, dispersants as processing aids to enhancewetting and therefore produce a uniform batch. The resulting plasticmaterial is then molded, in particular using an extrusion press or anextruder including an extrusion die, and the resulting moldings aredried and calcined. The organic additives are “burnt out” duringcalcinations of the extruded solid body. An activated molecular sieve,the catalytically active calcined product, can also be washcoated orotherwise applied to the extruded solid body as one or more sub-layersthat reside on the surface or penetrate wholly or partly into theextruded solid body.

The binder/matrix component is preferably selected from the groupconsisting of cordierite, nitrides, carbides, borides, intermetallics,lithium aluminosilicate, a spinel, an optionally doped alumina, a silicasource, titania, zirconia, titania-zirconia, zircon and mixtures of anytwo or more thereof. The paste can optionally contain reinforcinginorganic fibers selected from the group consisting of carbon fibers,glass fibers, metal fibers, boron fibers, alumina fibers, silica fibers,silica-alumina fibers, silicon carbide fibers, potassium titanatefibers, aluminum borate fibers and ceramic fibers.

The alumina binder/matrix component is preferably gamma alumina, but canbe any other transition alumina, i.e., alpha alumina, beta alumina, chialumina, eta alumina, rho alumina, kappa alumina, theta alumina, deltaalumina, lanthanum beta alumina and mixtures of any two or more suchtransition aluminas. It is preferred that the alumina is doped with atleast one non-aluminum element to increase the thermal stability of thealumina. Suitable alumina dopants include silicon, zirconium, barium,lanthanides and mixtures of any two or more thereof. Suitable lanthanidedopants include La, Ce, Nd, Pr, Gd and mixtures of any two or morethereof.

Preferably, an activated molecular sieve, is dispersed throughout, andpreferably evenly throughout, the entire extruded catalyst body.

Where any of the above extruded solid bodies are made into a wall-flowfilter, the porosity of the wall-flow filter can be from 30-80%, such asfrom 40-70%. Porosity and pore volume and pore radius can be measurede.g. using mercury intrusion porosimetry.

In a fifth aspect of the invention, an exhaust system for treatingexhaust gases from an engine can comprise: (a) a catalyst articlecomprising an activated H-form of a molecular sieve of the second aspectof the invention and at least one extra-framework metal selected fromthe group consisting of Ag, Au, Ce, Co, Cr, Cu, Fe, Ga, In, Ir, Mn, Mo,Ni, Os, Pd, Pt, Re, Rh, Ru, Sn and Zn, preferably Cu, Fe, Co and Ni,more preferably Cu and Fe, most preferably Cu, disposed downstream fromthe engine; (b) a source of a reductant, such as ammonia or ureaupstream of said catalyst article; and (c) an exhaust gas conduit forcarrying the exhaust gases from the engine to said catalyst article.

In some embodiments, the activated H-form of molecular sieve of thesecond aspect of the invention can be an SCR or an ammonia oxidationcomponent.

The system can include a controller for metering of nitrogenousreductant into the flowing exhaust gas only when it is determined thatthe catalyst is capable of catalyzing NO_(x) reduction at or above adesired efficiency, such as at temperatures above 100° C., above 150° C.or above 175° C. This determination can be assisted by one or moresuitable sensor inputs indicative of a condition of the engine selectedfrom the group consisting of: exhaust gas temperature, catalyst bedtemperature, accelerator position, mass flow of exhaust gas in thesystem, manifold vacuum, ignition timing, engine speed, lambda value ofthe exhaust gas, the quantity of fuel injected in the engine, theposition of the exhaust gas recirculation (EGR) valve and thereby theamount of EGR and boost pressure.

In a particular embodiment, metering can be controlled in response tothe quantity of nitrogen oxides in the exhaust gas determined eitherdirectly (using a suitable NO_(x) sensor) or indirectly, such as usingpre-correlated look-up tables or maps—stored in the controlmeans—correlating any one or more of the abovementioned inputsindicative of a condition of the engine with predicted NO_(x) content ofthe exhaust gas. The metering of the nitrogenous reductant can bearranged such that 60% to 200% of theoretical ammonia is present inexhaust gas entering the SCR catalyst calculated at 1:1 NH₃/NO and 4:3NH₃/NO₂. The control means can comprise a pre-programmed processor suchas an electronic control unit (ECU).

An exhaust system for internal combustion engines can comprise a passiveNO_(x) adsorber. The exhaust system preferably comprises one or moreadditional after-treatment devices capable of removing pollutants frominternal combustion engine exhaust gases at normal operatingtemperatures. Preferably, the exhaust system comprises the passiveNO_(x) adsorber and one or more other catalyst components selected from:(1) a selective catalytic reduction (SCR) catalyst, (2) a particulatefilter, (3) a SCR filter, (4) a NO_(x) adsorber catalyst, (5) athree-way catalyst, (6) an oxidation catalyst, or any combinationthereof. The passive NO_(x) adsorber is preferably a separate componentfrom any of the above after-treatment devices. Alternatively, thepassive NO_(x) adsorber can be incorporated as a component into any ofthe above after-treatment devices.

These after-treatment devices are well known in the art. Selectivecatalytic reduction (SCR) catalysts are catalysts that reduce NO_(x) toN₂ by reaction with nitrogen compounds (such as ammonia or urea) orhydrocarbons (lean NO_(x) reduction). A typical SCR catalyst iscomprised of a vanadia-titania catalyst, a vanadia-tungsta-titaniacatalyst, or a metal/zeolite catalyst such as iron/beta zeolite,copper/beta zeolite, copper/SSZ-13, copper/SAPO-34, Fe/ZSM-5, orcopper/ZSM-5.

Particulate filters are devices that reduce particulates from theexhaust of internal combustion engines. Particulate filters includecatalyzed particulate filters and bare (non-catalyzed) particulatefilters. Catalyzed particulate filters (for diesel and gasolineapplications) include metal and metal oxide components (such as Pt, Pd,Fe, Mn, Cu, and Ce) to oxidize hydrocarbons and carbon monoxide inaddition to destroying soot trapped by the filter.

Selective catalytic reduction filters (SCRF) are single-substratedevices that combine the functionality of an SCR and a particulatefilter. They are used to reduce NO_(x) and particulate emissions frominternal combustion engines. In addition to the SCR catalyst coating,the particulate filter can also include other metal and metal oxidecomponents (such as Pt, Pd, Fe, Mn, Cu, and ceria) to oxidizehydrocarbons and carbon monoxide in addition to destroying soot trappedby the filter. NO_(x) adsorber catalysts (NACs) are designed to adsorbNO_(x) under lean exhaust conditions, release the adsorbed NO_(x) underrich conditions, and reduce the released NO_(x) to form N₂. NACstypically include a NO_(x)-storage component (e.g., Ba, Ca, Sr, Mg, K,Na, Li, Cs, La, Y, Pr, and Nd), an oxidation component (preferably Pt)and a reduction component (preferably Rh). These components arecontained on one or more supports.

Three-way catalysts (TWCs) are typically used in gasoline engines understoichiometric conditions in order to convert NO_(x) to N₂, carbonmonoxide to CO₂, and hydrocarbons to CO₂ and H₂O on a single device.

Oxidation catalysts, and in particular diesel oxidation catalysts(DOCS), are well-known in the art. Oxidation catalysts are designed tooxidize CO to CO₂ and gas phase hydrocarbons (HC) and an organicfraction of diesel particulates (soluble organic fraction) to CO₂ andH₂O. Typical oxidation catalysts include platinum and optionally alsopalladium on a high surface area inorganic oxide support, such asalumina, silica-alumina and a zeolite.

The exhaust system can be configured so that the passive NO_(x) adsorberis located close to the engine and the additional after-treatmentdevice(s) are located downstream of the passive NO_(x) adsorber. Thus,under normal operating conditions, engine exhaust gas first flowsthrough the passive NO_(x) adsorber prior to contacting theafter-treatment device(s). Alternatively, the exhaust system can containvalves or other gas-directing means such that during the low temperatureperiod (below a temperature ranging from about 150 to 220° C.,preferably 200° C., about as measured at the after-treatment device(s)),the exhaust gas is directed to contact the after-treatment device(s)before flowing to the passive NO_(x) adsorber. Once the after-treatmentdevice(s) reaches the operating temperature (about 150 to 220° C.,preferably 200° C., as measured at the after-treatment device(s)), theexhaust gas flow is then redirected to contact the passive NO_(x)adsorber prior to contacting the after-treatment device(s). This ensuresthat the temperature of the passive NO_(x) adsorber remains low for alonger period of time, and thus improves efficiency of the passiveNO_(x) adsorber, while simultaneously allowing the after-treatmentdevice(s) to more quickly reach operating temperature. U.S. Pat. No.5,656,244, the teachings of which are incorporated herein by reference,for example, teaches means for controlling the flow of the exhaust gasduring cold-start and normal operating conditions.

In a sixth aspect of the invention, a method for synthesizing an SDAcontaining molecular sieve of the first aspect of the inventioncomprises:

-   -   a. forming a reaction mixture comprising: (i) at least one        source of aluminum, (ii) at least one source of silicon, (iii)        at least one source of alkaline or alkaline-earth cations        and (iv) one or more structure directing agents;    -   b. heating the reaction mixture;    -   c. forming molecular sieve crystals having an intergrowth and        the structure directing agent as described herein, and    -   d. recovering at least a portion of the molecular sieve crystals        from the reaction mixture.

Many aluminum compounds and their mixtures are suitable for use as theat least one source of alumina in the present invention. The aluminumcompounds include, but are not necessarily limited to aluminum oxide,boehmite, pseudo boehmite, aluminum hydroxy chloride, aluminum alkoxidessuch as aluminum tri-isopropoxide, aluminum tri-ethoxide, aluminumtri-n-butoxide and aluminum tri-isobutoxide, and mixtures thereof. Apreferred aluminum component is selected from the group consisting ofaluminum hydroxide, boehmite and pseudo boehmite.

The at least one source of alumina can comprise aluminum alkoxides,aluminum phosphates, aluminum hydroxide, sodium aluminate,pseudoboehmite, hydrated alumina, organoalumina, colloidal alumina,zeolite Y and mixtures thereof.

A number of silicon compounds and their mixtures may be used as thesilicon component for the method of the present invention. The siliconcompounds include, but are not limited to silica sol silica gel,colloidal silica, fumed silica, silicic acid, tetraethyl silicate,tetramethyl silicate, an alkoxide, a silicate, a tetraalkylorthosilicate, an aqueous colloidal suspension of silica and mixturesthereof. A preferred silicon component comprises a material selectedfrom the group consisting of silica sol, silica gel, colloidal silica,fumed silica, silicic acid, and mixtures thereof.

The source of alkaline or alkaline-earth cations may be any source ofthese elements, preferably selected from a source of Na, K andcombinations thereof.

SDA-1 is an N,N-dimethyl-3,5-dimethylpiperidinium cation or anN,N-diethyl-2,6-dimethylpiperidinium cation. SDA-2 is a CHA generatingSDA, such as a trimethyladmandylammonium cation. SDA-3 is a AFXgenerating SDA, such as 1,3-bis(1-adamantyl)imidazolium cation. SDA-2and or SDA-3 can be added to control the proportion of cha and aft andconsequently the “sfw-GME tail”.

The cation of the structure directing agent can be associated with ananion selected from the group consisting of acetate, bicarbonate,bromide, carbonate, carboxylate, chloride, fluoride, hydroxide, iodide,sulfate and tetrafluoroborate or combinations thereof. Preferably theanion is hydroxide.

The reaction mixture can have a molar compositional ratio of:

Components Ratio Preferred Ratio MeO₂/A₂O₃ 10-100 20-50 (SDA-1 + SDA-2 +SDA-3)/A₂O₃ 1-6  1.0-3.0 SDA-2/SDA-1  0-100 0.00-15.0 SDA-3/SDA-1  0-1000.00-15.0 X₂O/A₂O₃ 5.0-20.0 7.5-15  [OH⁻]/A₂O₃ 10.0-30.0  16.0-30 H₂O/A₂O₃ 100-2000 200-800

-   -   where Me is Si, Ge, Sn, Ti or combinations thereof and is        calculated as being in the oxide form (MO₂); A is Al, Fe, Cr, B,        Ga or combinations thereof and is calculated as being in the        oxide form (A₂O₃); X is Na, K or a combination thereof and is        calculated as being in the oxide form (X₂O); [OH⁻] is calculated        being as the sum of hydroxide ions brought by all components;        SDA-1 is an N,N-dimethyl-3,5-dimethylpiperidinium cation or an        N,N-diethyl-2,6-dimethylpiperidinium cation, SDA-2 is a CHA        generating SDA, such as a trimethyladmandylammonium cation, a        tetraethylammonium cation, a trimethylbenzylammonium cation, a        trimethylcyclohexylammonium cation or a        trimethyl(cyclohexylmethyl)ammonium or a phenyltrimethylammonium        cation and SDA-3 is a AFX generating SDA, such as a        1,3-bis(1-adamantyl)imidazolium,        1,1-(butane-1,4-diyl)bis-(quinuclidin-1-ium),        1,1-(pentane-1,5-diyl)bis-(quinuclidin-1-ium),        1,1′-(1,4-butanediyl)bis(4-aza-1-azoniabicyclo[2.2.2]octane),        1,1′-(1,5-pentanediyl)bis(4-aza-1-azoniabicyclo[2.2.2]octane).

The reaction mixture can further comprise from about 0.1 to about 10%w/w of seed crystals, wherein the seed crystals comprise a crystallinemolecular sieve having an AEI, AFX, AFT, CHA, GME or an SFW frameworkand/or an intergrowth having a JMZ-11, JMZ-11B or JMZ-11C framework.

A solvent can be mixed with the structure directing agent before thestructure directing agent is added to the reaction mixture. Preferably,the structure directing agent is completely mixable with, or soluble in,the solvent. Suitable solvents include but are not necessarily limitedto water, methanol, ethanol, n-propanol, iso-propanol, C₄ alcohols,ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol and mixturesthereof. A preferred solvent comprises water.

The silica component can be mixed in a suitable solvent to form a firstmixture of uniform composition and texture. Adequate mixing, stirring,or agitation usually can be used. The aluminum component can be added tothis mixture, followed by the structure directing agent.

In order to make an SDA containing intergrowth, the molar ratios of thecomponents in the mixture must be controlled and maintained. Beforebeing subjected to conditions effective to produce the molecular sieveproduct, the final reaction mixture, excluding any other organic orinorganic moieties or species which may be present, has a molarcompositional ratio of:

Components Ratio Preferred Ratio MeO₂/A₂O₃ 10-100 20-50 (SDA-1 + SDA-2 +SDA-3)/A₂O₃ 1-6  1.0-3.0 SDA-2/SDA-1  0-100 0.00-15.0 SDA-3/SDA-1  0-1000.00-15.0 X₂O/A₂O₃ 5.0-20.0 7.5-15  [OH⁻]/A₂O₃ 10.0-30.0  16.0-30 H₂O/A₂O₃ 100-2000 200-800

-   -   where Me is Si, Ge, Sn, Ti or combinations thereof and is        calculated as being in the oxide form (MO₂); A is Al, Fe, Cr, B,        Ga or combinations thereof and is calculated as being in the        oxide form (A₂O₃); X is Na, K or a combination thereof and is        calculated as being in the oxide form (X₂O); [OH⁻] is calculated        being as the sum of hydroxide ions brought by all components;        SDA-1 is an N,N-dimethyl-3,5-dimethylpiperidinium cation or an        N,N-diethyl-2,6-dimethylpiperidinium cation, SDA-2 is a CHA        generating SDA, such as a trimethyladmandylammonium cation, a        tetraethylammonium cation, a trimethylbenzylammonium cation, a        trimethylcyclohexylammonium cation or a        trimethyl(cyclohexylmethyl)ammonium or a phenyltrimethylammonium        cation and SDA-3 is a AFX generating SDA, such as a        1,3-bis(1-adamantyl)imidazolium,        1,1-(butane-1,4-diyl)bis-(quinuclidin-1-ium),        1,1-(pentane-1,5-diyl)bis-(quinuclidin-1-ium),        1,1′-(1,4-butanediyl)bis(4-aza-1-azoniabicyclo[2.2.2]octane),        1,1′-(1,5-pentanediyl)bis(4-aza-1-azoniabicyclo[2.2.2]octane).

It is preferable to use adequate mixing, blending, stirring, oragitation to provide a uniform composition throughout the mixture. Theuse of a concentration or composition gradient should be minimizedbecause such a gradient could result in the formation of differentmolecular sieve products.

Preferably, a constant temperature can be maintained during thepreparation of the mixture. Cooling or heating may be required toprovide a constant temperature environment. A suitable temperature forpreparation of a mixture can be in the range of from about 15° C. toabout 80° C., preferably from about 20° C. to about 50° C. Pressure isusually not critical for preparing a mixture unless one or more gasesare used to control other reaction parameters, such as pH, temperature,or concentration.

Preferably, the overall process will have an overall yield on silica ofat least about 60%, for Example at least about 70%, at least about 80%.

The reaction mixture can be in the form of a solution, a colloidaldispersion (colloidal sol), gel, or paste, with a gel being preferred.

Generally, the reaction mixture can be maintained at an elevatedtemperature until the SDA containing intergrowth crystals are formed.The hydrothermal crystallization is usually conducted under autogenouspressure, at a temperature between about 100-220° C., for examplebetween about 150 and 200° C., for duration of several hours, forexample, about 0.1-10 days, and preferably from about 1-7 days.

During the hydrothermal crystallization step, crystals of theintergrowth can be allowed to nucleate spontaneously from the reactionmixture. The use of intergrowth crystals as seed material can beadvantageous in decreasing the time necessary for completecrystallization to occur. When used as seeds, intergrowth crystals canbe added in an amount between 0.1 and 10% of the weight of silica usedin the reaction mixture.

Once the SDA containing intergrowth crystals have formed, the solidproduct can be separated from the reaction mixture by standardseparation techniques such as filtration. The SDA containing intergrowthcrystals can be water-washed and then dried, for several second to a fewminutes (e.g., 5 second to 10 minutes for flash drying) or several hours(e.g., about 4-24 hours for oven drying at 75-150° C.), to obtain SDAcontaining intergrowth crystals. The drying step can be performed atatmospheric pressure or under vacuum.

It will be appreciated that the foregoing sequence of steps, as well aseach of the above-mentioned periods of time and temperature values aremerely exemplary and may be varied.

The intergrowth crystals produced in accordance with the methodsdescribed herein can have a mean crystalline size of about 0.01 to about20 μm, for example about 0.01 to about 5 μm, about 0.2 to about 1 μm,and about 0.25 to about 0.5 μm, where the endpoints can be included.Large crystals can be milled using a jet mill or otherparticle-on-particle milling technique to an average size of about 1.0to about 1.5 micron to facilitate washcoating a slurry containing thecatalyst to a substrate, such as a flow-through monolith.

The reaction mixture for intergrowth synthesis process typicallycontains at least one source of aluminum, at least one structuredirecting agent (SDA-1), where in (SDA-1) comprises anN,N-dimethyl-3,5-dimethylpiperidinium cation or anN,N-diethyl-2,6-dimethylpiperidinium cation, at least one source ofsilicon, and at least one source of an alkaline metal or an alkalineearth metal. The composition can further comprise a second SDA (SDA-2)and or a third SDA (SDA-3). SDA-2 is a CHA generating SDA, such as atrimethyladmandylammonium cation, a tetraethylammonium cation, atrimethylbenzylammonium cation, a trimethylcyclohexylammonium cation ora trimethyl(cyclohexylmethyl)ammonium or a phenyltrimethylammoniumcation. SDA-3 is a AFX generating SDA, such as a1,3-bis(1-adamantyl)imidazolium,1,1-(butane-1,4-diyl)bis-(quinuclidin-1-ium),1,1-(pentane-1,5-diyl)bis-(quinuclidin-1-ium),1,1′-(1,4-butanediyl)bis(4-aza-1-azoniabicyclo[2.2.2]octane),1,1′-(1,5-pentanediyl)bis(4-aza-1-azoniabicyclo[2.2.2]octane).

The synthesis methods described herein are not necessarily limited toforming metaloaluminosilicates, but can also be applied to synthesizeother compositions of JMZ-11 such as molecular sieves comprisingphosphorus in the frame work, such as aluminophosphates (AlPO), ametal-substituted aluminophosphates (MeAlPO), a silico-aluminophosphates(SAPO), or a metal substituted silico-aluminophosphates.

In a seventh aspect of the invention, methods of synthesizing anactivated molecular sieve from an activated molecular sieve whichcomprises an SDA, are described. An activated molecular sieve is lackingthe structure directing agent that is present in an activated molecularsieve of the first aspect of the invention. An activated molecular sievecan have the SDA removed by calcination or treatment with a peroxide.

An activated molecular sieve can be produced by calcining an intergrowthcomprising two or more SDAs at a temperature and for a period of timesufficient to remove the structure directing agent and form an activatedmolecular sieve. An activated molecular sieve can be calcined at300-700° C., preferably at 400 to 650° C. in the presence of anoxygen-containing gas (such as air) when it is desirable to oxidize theSDAs. In some case, where a reducing environment is preferred,calcination is performed using an inert gas. The inert gas can be anygas that is substantially free of oxygen (less than 1 vol. % oxygen,preferably less than 0.1 vol. % oxygen), most preferably oxygen-free.Preferably, the inert gas is nitrogen, argon, neon, helium, carbondioxide, or the like, and mixture thereof. The calcination is preferablyperformed for greater than 1 hour.

The production of an activated molecular sieve of the second aspect ofthe convention can comprise first forming SDA containing intergrowth ofthe first aspect of the invention and then converting the SDA containingintergrowth to an activated molecular sieve.

In an eighth aspect of the invention, a composition for manufacturing anSDA containing intergrowth comprises the following materials in thecorresponding ratios:

Components Ratio Preferred Ratio MeO₂/A₂O₃ 10-100 20-50 (SDA-1 + SDA-2 +SDA-3)/A₂O₃ 1-6  1.0-3.0 SDA-2/SDA-1  0-100 0.00-15.0 SDA-3/SDA-1  0-1000.00-15.0 X₂O/A₂O₃ 5.0-20.0 7.5-15  [OH⁻]/A₂O₃ 10.0-30.0  16.0-30 H₂O/A₂O₃ 100-2000 200-800

-   -   where Me is Si, Ge, Sn, Ti or combinations thereof and is        calculated as being in the oxide form (MO₂); A is Al, Fe, Cr, B,        Ga or combinations thereof and is calculated as being in the        oxide form (A₂O₃); X is Na, K or a combination thereof and is        calculated as being in the oxide form (X₂O); [OH⁻] is calculated        being as the sum of hydroxide ions brought by all components;        SDA-1 is an N,N-dimethyl-3,5-dimethylpiperidinium cation or an        N,N-diethyl-2,6-dimethylpiperidinium cation, SDA-2 is a CHA        generating SDA, such as a trimethyladmandylammonium cation, a        tetraethylammonium cation, a trimethylbenzylammonium cation, a        trimethylcyclohexylammonium cation or a        trimethyl(cyclohexylmethyl)ammonium or a phenyltrimethylammonium        cation and SDA-3 is a AFX generating SDA, such as a        1,3-bis(1-adamantyl)imidazolium,        1,1-(butane-1,4-diyl)bis-(quinuclidin-1-ium),        1,1-(pentane-1,5-diyl)bis-(quinuclidin-1-ium),        1,1′-(1,4-butanediyl)bis(4-aza-1-azoniabicyclo[2.2.2]octane),        1,1′-(1,5-pentanediyl)bis(4-aza-1-azoniabicyclo[2.2.2]octane).

A number of silicon compounds and their mixtures can be used as thesilicon component for the composition of the present invention. Thesilicon compounds include, but are not limited to silica sol silica gel,colloidal silica, fumed silica, silicic acid, tetraethyl silicate,tetramethyl silicate, and mixtures thereof. A preferred siliconcomponent comprises a material selected from the group consisting ofsilica sol, silica gel, colloidal silica, fumed silica, silicic acid,and mixtures thereof.

Many aluminum compounds and their mixtures are suitable for use as thealuminum component in the present invention. The aluminum compoundsinclude, but are not necessarily limited to aluminum oxide, boehmite,pseudo boehmite, aluminum hydroxy chloride, aluminum alkoxides such asaluminum tri-isopropoxide, aluminum tri-ethoxide, aluminumtri-n-butoxide and aluminum tri-isobutoxide, and mixtures thereof. Apreferred aluminum component is selected from the group consisting ofaluminum hydroxide, boehmite and pseudo boehmite.

The composition comprises a first SDA (SDA-1) and can further comprise asecond SDA (SDA-2) and or a third SDA (SDA-3). SDA-1 is aN,N-dimethyl-3,5-dimethylpiperidinium cation or anN,N-diethyl-2,6-dimethylpiperidinium cation. SDA-2 is a CHA generatingSDA, such as a trimethyladmandylammonium cation, a tetraethylammoniumcation, a trimethylbenzylammonium cation, a trimethylcyclohexylammoniumcation or a trimethyl(cyclohexylmethyl)ammonium or aphenyltrimethylammonium cation and SDA-3 is a AFX generating SDA, suchas a 1,3-bis(1-adamantyl)imidazolium,1,1-(butane-1,4-diyl)bis-(quinuclidin-1-ium),1,1-(pentane-1,5-diyl)bis-(quinuclidin-1-ium),1,1′-(1,4-butanediyl)bis(4-aza-1-azoniabicyclo[2.2.2]octane),1,1′-(1,5-pentanediyl)bis(4-aza-1-azoniabicyclo[2.2.2]octane).

The anion associated with the cation can be an acetate, bicarbonate,bromide, carbonate, carboxylate, chloride, fluoride, hydroxide, iodide,sulfate and tetrafluoroborate, or a combination thereof. Preferably theanion is hydroxide.

The composition can further comprise from about 0.1 to about 10% w/w ofseed crystals, wherein the seed crystals comprise a crystallinemolecular sieve having an AEI, AFX, AFT, CHA, GME or an SFW frameworkand/or an intergrowth having a JMZ-11, JMZ-11B or JMZ-11C framework.

In a ninth aspect of the invention, provided are methods of making anactivated molecular sieve from a molecular sieve comprising anintergrowth containing an SDA and alkali metal cations of the firstaspect of the invention. Usually it is desirable to remove the alkalimetal cation by ion exchange and replace it with hydrogen, ammonium, orany desired metal ion. Accordingly, zeolites of the present inventionmay be a Na-form zeolite, a K-form zeolite, or a combined Na, K-form andthe like, or may be an H-form zeolite, an ammonium-form zeolite, or ametal-exchanged zeolite. Typical ion exchange techniques involvecontacting the synthetic zeolite with a solution containing a salt ofthe desired replacing cation or cations. Although a wide variety ofsalts can be employed, chlorides and other halides, nitrates, sulfatesand carbonates are particularly preferred. Representative ion exchangetechniques are widely known in the art. Ion exchange occurspost-synthesis and can take place either before or after the zeolite iscalcined. Following contact with the salt solution of the desiredreplacing cation, the zeolite is typically washed with water and driedat temperatures ranging from 65° C. to about 315° C., usually between80° C. and 150° C. After washing, the zeolite can be calcined in aninert gas and/or air at temperature ranging from about 315° C. to 850°C. for periods of time ranging from 1 to 48 hours, or more, to produce acatalytically active and stable product.

In a tenth aspect of the invention, provided are methods for treating anexhaust gas from an engine by contacting the exhaust gas with anactivated molecular sieve of the second aspect of the invention asherein before described. The methods can be used for the reduction ofNO_(x) compounds and/or oxidation of NH₃ in a gas, which comprisescontacting the gas with an activated molecular sieve or a metalcontaining activated molecular sieve for a time sufficient to reduce thelevel of NO_(x) compounds in the gas.

A method for treating an exhaust gas comprises contacting a combustionexhaust gas containing NO_(x) and/or NH₃ with an activated H-form of amolecular sieve as described herein to selectively reduce at least aportion of the NO_(x) into N₂ and H₂O and/or oxidize at least a portionof the NH₃.

A method for treating an exhaust gas comprising contacting a combustionexhaust gas containing NO_(x) with a passive NO_(x) absorber comprisingan activated H-form of a molecular sieve as described herein.

A method for treating an exhaust gas comprising contacting a combustionexhaust gas containing NH₃ with a passive NO_(x) absorber comprising anactivated H-form of a molecular sieve as described herein.

An activated molecular sieve or a metal containing activated molecularsieve can promote the reaction of a reductant, preferably ammonia, withnitrogen oxides to selectively form elemental nitrogen (N₂) and water(H₂O). Thus, the catalyst can be formulated to favor the reduction ofnitrogen oxides with a reductant (i.e., an SCR catalyst). Examples ofsuch reductants include hydrocarbons (e.g., C3-C6 hydrocarbons) andnitrogenous reductants such as ammonia and ammonia hydrazine or anysuitable ammonia precursor, such as urea ((NH₂)₂CO), ammonium carbonate,ammonium carbamate, ammonium hydrogen carbonate or ammonium formate.

An activated molecular sieve, or a metal containing activated molecularsieve, can also promote the oxidation of ammonia. Preferably, anactivated molecular sieve contains one or more metal ions, such ascopper or iron, that are impregnated into an activated molecular sieve.The catalyst can be formulated to favor the oxidation of ammonia withoxygen, particularly a concentration of ammonia typically encountereddownstream of an SCR catalyst (e.g., ammonia oxidation (AMOX) catalyst,such as an ammonia slip catalyst (ASC)). An activated molecular sieve,or a metal containing an activated molecular sieve, can be disposed as atop layer over an oxidative under-layer, wherein the under-layercomprises a platinum group metal (PGM) catalyst or a non-PGM catalyst.Preferably, the catalyst component in the underlayer is disposed on ahigh surface area support, including but not limited to alumina.

SCR and AMOX operations can be performed in series, wherein bothprocesses utilize a catalyst comprising an activated molecular sieve, ora metal containing activated molecular sieve, as described herein, andwherein the SCR process occurs upstream of the AMOX process. Forexample, an SCR formulation of the catalyst can be disposed on the inletside of a filter and an AMOX formulation of the catalyst can be disposedon the outlet side of the filter.

Accordingly, provided is a method for the reduction of NO_(x) compoundsor oxidation of NH₃ in a gas, which comprises contacting the gas with acatalyst composition described herein for the catalytic reduction ofNO_(x) compounds for a time sufficient to reduce the level of NO_(x)compounds and/or NH₃ in the gas. A catalyst article can have an ammoniaslip catalyst disposed downstream of a selective catalytic reduction(SCR) catalyst. The ammonia slip catalyst can oxidize at least a portionof any nitrogenous reductant that is not consumed by the selectivecatalytic reduction process. The ammonia slip catalyst can be disposedon the outlet side of a wall flow filter and an SCR catalyst can bedisposed on the upstream side of a filter. The ammonia slip catalyst canbe disposed on the downstream end of a flow-through substrate and an SCRcatalyst can be disposed on the upstream end of the flow-throughsubstrate. The ammonia slip catalyst and SCR catalyst can be disposed onseparate bricks within the exhaust system. These separate bricks can beadjacent to, and in contact with, each other or separated by a specificdistance, provided that they are in fluid communication with each otherand provided that the SCR catalyst brick is disposed upstream of theammonia slip catalyst brick.

The SCR and/or AMOX process can be performed at a temperature of ≥100°C., preferably at a temperature from about 150° C. to about 750° C.,more preferably from about 175 to about 550° C., even more preferablyfrom 175 to 400° C.

In some conditions, the temperature range can be from 450 to 900° C.,preferably 500 to 750° C., more preferably 500 to 650° C., even morepreferably 450 to 550° C. Temperatures greater than 450° C. areparticularly useful for treating exhaust gases from a heavy and lightduty diesel engine that is equipped with an exhaust system comprising(optionally catalyzed) diesel particulate filters which are regeneratedactively, e.g. by injecting hydrocarbon into the exhaust system upstreamof the filter, wherein the molecular sieve catalyst for use in thepresent invention is located downstream of the filter.

Methods of the present invention can comprise contacting the exhaust gaswith one or more flow-through SCR catalyst device(s) in the presence ofa reducing agent to reduce the NO_(x) concentration in the exhaust gasand one or more of the following steps: (a) accumulating and/orcombusting soot that is in contact with the inlet of a catalytic filter;(b) introducing a nitrogenous reducing agent into the exhaust gas streamprior to contacting the catalytic filter, preferably with no interveningcatalytic steps involving the treatment of NO_(x) and the reductant; (c)generating NH₃ over a NO_(x) adsorber catalyst or lean NO_(x) trap, andpreferably using such NH₃ as a reductant in a downstream SCR reaction;(d) contacting the exhaust gas stream with a DOC to oxidize hydrocarbonbased soluble organic fraction (SOF) and/or carbon monoxide into CO₂,and/or oxidize NO into NO₂, which in turn, can be used to oxidizeparticulate matter in particulate filter; and/or reduce the particulatematter (PM) in the exhaust gas; and (e) contacting the exhaust gas withan ammonia slip catalyst, preferably downstream of the SCR catalyst tooxidize most, if not all, of the ammonia prior to emitting the exhaustgas into the atmosphere or passing the exhaust gas through arecirculation loop prior to exhaust gas entering/re-entering the engine.

All, or at least a portion of, the nitrogen-based reductant,particularly NH₃, for consumption in the SCR process can be supplied bya NO_(x) adsorber catalyst (NAC), a lean NO_(x) trap (LNT), or a NO_(x)storage/reduction catalyst (NSRC), disposed upstream of the SCRcatalyst, e.g., a SCR catalyst of the present invention disposed on awall-flow filter. NAC components useful in the present invention includea catalyst combination of a basic material (such as alkali metal,alkaline earth metal or a rare earth metal, including oxides of alkalimetals, oxides of alkaline earth metals, and combinations thereof), anda precious metal (such as platinum), and optionally a reduction catalystcomponent, such as rhodium. Specific types of basic material useful inthe NAC include cesium oxide, potassium oxide, magnesium oxide, sodiumoxide, calcium oxide, strontium oxide, barium oxide, and combinationsthereof. The precious metal is preferably present at about 10 to about200 g/ft³, such as 20 to 60 g/ft³. Alternatively, the precious metal ofthe catalyst is characterized by the average concentration which can befrom about 40 to about 100 grams/ft³.

During periodically rich regeneration events, NH₃ can be generated overa NO_(x) adsorber catalyst. The SCR catalyst downstream of the NO_(x)adsorber catalyst can improve the overall system NO_(x) reductionefficiency. In the combined system, the SCR catalyst is capable ofstoring the released NH₃ from the NAC catalyst during rich regenerationevents and utilizes the stored NH₃ to selectively reduce some or all ofthe NO_(x) that slips through the NAC catalyst during the normal leanoperation conditions.

The method for treating exhaust gas as described herein can be performedon an exhaust gas derived from a combustion process, such as from aninternal combustion engine (whether mobile or stationary), a gas turbineand coal or oil fired power plants. The method can also be used to treatgas from industrial processes such as refining, from refinery heatersand boilers, furnaces, the chemical processing industry, coke ovens,municipal waste plants and incinerators, etc. The method can be used fortreating exhaust gas from a vehicular lean burn internal combustionengine, such as a diesel engine, a lean-burn gasoline engine or anengine powered by liquid petroleum gas or natural gas.

A method for treating an exhaust gas can comprise contacting acombustion exhaust gas containing NO_(x) with a passive NO_(x) absorbercomprising an activated molecular sieve of the second aspect of theinvention, as herein before described. A passive NO_(x) adsorbereffective to adsorb NO_(x) at or below a low temperature and release theadsorbed NO_(x) at temperatures above the low temperature can comprise anoble metal and an activated molecular sieve. The noble metal can beselected from the group consisting of platinum, palladium, rhodium,gold, silver, iridium, ruthenium, osmium, and mixtures thereof, and ispreferably palladium.

The passive NO_(x) adsorber can be effective to adsorb NO_(x) at, orbelow, a low temperature (preferably less than 250° C., more preferablyabout 200° C.) and release the adsorbed NO_(x) at temperatures above thelow temperature. The passive NO_(x) adsorber comprises a noble metal andan activated molecular sieve. The noble metal is selected from the groupconsisting of palladium, platinum, rhodium, gold, silver, iridium,ruthenium, osmium, or mixtures thereof; more preferably, palladium,platinum, rhodium, or mixtures thereof. Palladium is particularlypreferred.

The passive NO_(x) adsorber can be prepared by any known means. Forinstance, the noble metal can be added to an activated molecular sieveto form the passive NO_(x) adsorber by any known means, the manner ofaddition is not considered to be particularly critical. For Example, anoble metal compound (such as palladium nitrate) can be supported on anactivated molecular sieve by impregnation, adsorption, ion-exchange,incipient wetness, precipitation, or the like. Other metals can also beadded to the passive NO_(x) adsorber. Preferably, some of the noblemetal (more than 1 percent of the total noble metal added) in thepassive NO_(x) adsorber is located inside the pores of an activatedmolecular sieve. More preferably, more than 5 percent of the totalamount of noble metal is located inside the pores of an activatedmolecular sieve; and even more preferably can be greater than 10 percentor greater than 25% or greater than 50 percent of the total amount ofnoble metal that is located inside the pores of an activated molecularsieve.

Preferably, the passive NO_(x) adsorber further comprises a flow-throughsubstrate or filter substrate. The passive NO_(x) adsorber can be coatedonto the flow-through or filter substrate, and preferably deposited onthe flow-through or filter substrate using a washcoat procedure toproduce a passive NO_(x) adsorber system.

The flow-through or filter substrate can be a substrate that is capableof containing catalyst components. The substrate is preferably a ceramicsubstrate or a metallic substrate. The ceramic substrate can be made ofany suitable refractory material, e.g., alumina, silica, titania, ceria,zirconia, magnesia, molecular sieves, preferably a zeolite, morepreferable an aluminosilicate, silicon nitride, silicon carbide,zirconium silicates, magnesium silicates, aluminosilicates, metalloaluminosilicates (such as cordierite and spudomene), or a mixture ormixed oxide of any two or more thereof. Cordierite, a magnesiumaluminosilicate, and silicon carbide are particularly preferred.

The metallic substrates can be made of any suitable metal, and inparticular heat-resistant metals and metal alloys such as titanium andstainless steel as well as ferritic alloys containing iron, nickel,chromium, and/or aluminum in addition to other trace metals.

The flow-through substrate is preferably a flow-through monolith havinga honeycomb structure with many small, parallel thin-walled channelsrunning axially through the substrate and extending throughout from aninlet or an outlet of the substrate. The channel cross-section of thesubstrate can be any shape, but is preferably square, sinusoidal,triangular, rectangular, hexagonal, trapezoidal, circular, or oval.

The filter substrate is preferably a wall-flow monolith filter. Thechannels of a wall-flow filter are alternately blocked, which allow theexhaust gas stream to enter a channel from the inlet, then flow throughthe channel walls, and exit the filter from a different channel leadingto the outlet. Particulates in the exhaust gas stream are thus trappedin the filter.

The passive NO_(x) adsorber can be added to the flow-through or filtersubstrate by any known means. A representative process for preparing thepassive NO_(x) adsorber using a washcoat procedure is set forth below.It will be understood that the process below can be varied according todifferent embodiments of the invention.

The pre-formed passive NO_(x) adsorber can be added to the flow-throughor filter substrate by a washcoating step. Alternatively, the passiveNO_(x) adsorber can be formed on the flow-through or filter substrate byfirst washcoating unmodified small pore molecular sieve onto thesubstrate to produce a molecular sieve-coated substrate. Noble metal canthen be added to the activated molecular sieve-coated substrate, whichcan be accomplished by an impregnation procedure, or the like.

The washcoating procedure is preferably performed by first slurryingfinely divided particles of the passive NO_(x) adsorber (or unmodifiedsmall pore molecular sieve) in an appropriate solvent, preferably water,to form the slurry. Additional components, such as transition metaloxides, binders, stabilizers, or promoters can also be incorporated inthe slurry as a mixture of water soluble or water-dispersible compounds.The slurry preferably contains between 10 to 70 weight percent solids,more preferably between 20 to 50 weight percent. Prior to forming theslurry, the passive NO_(x) adsorber (or unmodified small pore molecularsieve) particles are preferably subject to a size reduction treatment(e.g., milling) such that the average particle size of the solidparticles is less than 20 microns in diameter.

The flow-through or filter substrate can then be dipped one or moretimes into the slurry or the slurry can be coated on the substrate suchthat there will be deposited on the substrate the desired loading ofcatalytic materials. If noble metal is not incorporated into anactivated molecular sieve prior to washcoating the flow-through orfilter substrate, the activated molecular sieve-coated substrate istypically dried and calcined and then, the noble metal can be added tothe molecular sieve-coated substrate by any known means, includingimpregnation, adsorption, or ion-exchange, for example, with a noblemetal compound (such as palladium nitrate). Preferably, the entirelength of the flow-through or filter substrate is coated with the slurryso that a washcoat of the passive NO_(x) adsorber covers the entiresurface of the substrate.

After the flow-through or filter substrate has been coated with thepassive NO_(x) adsorber, and impregnated with noble metal if necessary,the coated substrate is preferably dried and then calcined by heating atan elevated temperature to form the passive NO_(x) adsorber-coatedsubstrate. Preferably, the calcination occurs at 400 to 600° C. forapproximately 1 to 8 hours.

The flow-through or filter substrate can be comprised of the passiveNO_(x) adsorber. In this case, the passive NO_(x) adsorber can beextruded to form the flow-through or filter substrate. The passiveNO_(x) adsorber extruded substrate is preferably a honeycombflow-through monolith.

Extruded molecular sieve substrates and honeycomb bodies, and processesfor making them, are known in the art. See, for example, U.S. Pat. Nos.5,492,883, 5,565,394, and 5,633,217 and U.S. Pat. No. Re. 34,804.Typically, the molecular sieve material is mixed with a permanent bindersuch as silicone resin and a temporary binder such as methylcellulose,and the mixture is extruded to form a green honeycomb body, which isthen calcined and sintered to form the final small pore molecular sieveflow-through monolith. The molecular sieve can contain the noble metalprior to extruding such that a passive NO_(x) adsorber monolith isproduced by the extrusion procedure. Alternatively, the noble metal canbe added to a pre-formed molecular sieve monolith in order to producethe passive NO_(x) adsorber monolith.

The invention also includes a method for treating exhaust gas from aninternal combustion engine using a passive NO_(x) adsorber comprising anactivated molecular sieve as herein before described. The methodcomprises adsorbing NO_(x) onto the passive NO_(x) adsorber attemperatures at or below 250° C., preferably below 200° C., thermallydesorbing NO_(x) from the passive NO_(x) adsorber at a temperature abovethe above stated temperature, and catalytically removing the desorbedNO_(x) on a catalyst component downstream of the passive NO_(x)adsorber.

The catalyst component downstream of the passive NO_(x) adsorber can bean SCR catalyst, a particulate filter, a SCR filter, a NO_(x) adsorbercatalyst, a three-way catalyst, an oxidation catalyst, or combinationsthereof.

In an eleventh aspect of the invention, provided is a method ofconverting methanol to an olefin (MTO) by contacting methanol with anactivated H-form molecular sieve comprising an intergrowth of the secondaspect of the invention as herein described.

In an eleventh aspect of the invention, provided is a method ofconverting an oxygenate, such as methanol, to an olefin (MTO) bycontacting methanol with an activated molecular sieve of the secondaspect of the invention as herein before described. The reaction processfor the conversion of an oxygenate to olefin (OTO) is well known in theart. Specifically, in an OTO reaction process, an oxygenate contacts amolecular sieve catalyst composition under conditions effective toconvert at least a portion of the oxygenate to light olefins. Whenmethanol is the oxygenate, the process is generally referred to as amethanol to olefin (MTO) reaction process. Methanol is a particularlypreferred oxygenate for the synthesis of ethylene and/or propylene.

A process for converting an oxygenate feed to a light olefin productcomprises: a) providing an oxygenate feed comprising a majority ofmethanol; b) providing a catalyst composition comprising an activatedmolecular sieve and optionally a basic metal oxide co-catalyst; and c)contacting the oxygenate feed with the catalyst composition underconditions sufficient to convert at least a portion of the oxygenatefeed to a light olefin product.

An oxygenate feedstock, particularly a mixed alcohol compositioncontaining methanol and ethanol, is a useful feedstock for a variety ofcatalytic processes, particularly oxygenate to olefin (OTO) reactionprocesses, in which a catalyst composition, typically containing aprimary oxide catalyst having at least two of Al, Si, and P (e.g., analuminosilicate molecular sieve, preferably a high-silicaaluminosilicate molecular sieve) and preferably a basic metal oxideco-catalyst, can be used to convert the oxygenate feedstock into a lightolefin product, e.g., containing ethylene and/or propylene, preferablyincluding ethylene. The olefins can then be recovered and used forfurther processing, e.g., in the manufacture of polyolefins such aspolyethylene and/or polypropylene, olefin oligomers, olefin copolymers,mixtures thereof, and/or blends thereof.

One or more additional components can be included in the feedstock thatis directed to the OTO reaction system. For example, a feedstockdirected to the OTO reaction system can optionally contain, in additionto methanol and ethanol, one or more aliphatic-containing compounds suchas alcohols, amines, carbonyl compounds for example aldehydes, ketonesand carboxylic acids, ethers, halides, mercaptans, sulfides, and thelike, and mixtures thereof. The aliphatic moiety of thealiphatic-containing compounds typically contains from 1 to 50 carbonatoms, preferably from 1 to 20 carbon atoms, more preferably from 1 to10 carbon atoms, most preferably from 1 to 4 carbon atoms.

Non-limiting examples of aliphatic-containing compounds include:alcohols such as methanol, ethanol, n-propanol, isopropanol, and thelike, alkyl-mercaptans such as methyl mercaptan and ethyl mercaptan,alkyl-sulfides such as methyl sulfide, alkyl amines such as methylamine, alkyl ethers such as DME, diethyl ether and methyl ethyl ether,alkyl-halides such as methyl chloride and ethyl chloride, alkyl ketonessuch as dimethyl ketone, alkyl-aldehydes such as formaldehyde andacetaldehyde, and various organic acids such as formic acid and aceticacid.

The various feedstocks discussed above are converted primarily into oneor more olefins. The olefins or olefin monomers produced from thefeedstock typically have from 2 to 30 carbon atoms, preferably 2 to 8carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably2 to 4 carbons atoms, and most preferably ethylene and/or propylene.Non-limiting examples of olefin monomer(s) include ethylene, propylene,butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1 and decene-1,preferably ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1,hexene-1, octene-1 and isomers thereof. Other olefin monomers caninclude, but are not limited to, unsaturated monomers, diolefins having4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes,vinyl monomers, and cyclic olefins.

A catalyst article for converting a low molecular weight oxygencontaining species to an olefin rich hydrocarbon stream can comprise anactivated molecular sieve, where the activated molecular sieve isdisposed on a support and/or within a structure.

A catalyst article for converting a low molecular weight oxygencontaining species to an aromatic rich hydrocarbon stream can comprisean activated molecular sieve, where the activated molecular sieve isdisposed on a support and/or within a structure.

The catalyst can be incorporated or mixed with other additive materials.Such an admixture is typically referred to as formulated catalyst or ascatalyst composition. Preferably, the additive materials aresubstantially inert to conversion reactions involving dialkyl ethers(e.g., dimethyl ether) and/or alkanols (e.g., methanol, ethanol, and thelike).

One or more other materials can be mixed with an activated molecularsieve, particularly a material that is resistant to the temperatures andother conditions employed in organic conversion processes. Suchmaterials can include catalytically active and inactive materials andsynthetic or naturally occurring zeolites, as well as inorganicmaterials such as clays, silica, and/or other metal oxides such asalumina. The latter may be either naturally occurring or in the form ofgelatinous precipitates or gels including mixtures of silica and metaloxides. Use of a catalytically active material can tend to change theconversion and/or selectivity of the catalyst in the oxygenateconversion process. Inactive materials suitably can serve as diluents tocontrol the amount of conversion in the process so that products can beobtained in an economic and orderly manner without employing other meansfor controlling the rate of reaction. These materials can beincorporated into naturally occurring clays, e.g., bentonite and kaolin,to improve the crush strength of the catalyst under commercial operatingconditions. The materials (e.g., clays, oxides, etc.) can function asbinders for the catalyst. It can be desirable to provide a catalysthaving good crush strength, because, in commercial use, it can bedesirable to prevent the catalyst from breaking down into powder-likematerials.

Naturally occurring clays that can be employed can include, but are notlimited to, the montmorillonite and kaolin family, which familiesinclude the subbentonites, and the kaolins commonly known as Dixie,McNamee, Georgia and Florida clays, or others in which the main mineralconstituent includes halloysite, kaolinite, dickite, nacrite, oranauxite. Such clays can be used in the raw state as originally mined orinitially subjected to calcination, acid treatment, or chemicalmodification. Other useful binders can include, but are not limited to,inorganic oxides such as silica, titania, beryllia, alumina, andmixtures thereof.

In addition to the foregoing materials, an activated molecular sieve canbe composited with a porous matrix material such as silica-alumina,silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia andsilica-titania as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesiaand silica-magnesia-zirconia.

The relative proportions of an activated molecular sieve and aninorganic oxide matrix can vary widely. For example, a mixture caninclude a zeolite content ranging from about 1 to about 90 percent byweight and more usually, particularly when the composite is prepared inthe form of beads, in the range from about 2 to about 80 weight percentof the composite.

The invention also relates to C2, C3, C4 and C5 products formed by OTOor MTO application using an activated molecular sieve as a catalyst orco-catalyst.

The following examples demonstrate, but do not limit, aspects of thepresent invention.

EXAMPLES Example 1—Synthesis of SDA Containing JMZ-11A with Approximate54% cha Cavities, 23% aft Cavities and 23% “sfw-GME” Tail

7.27 g of sodium hydroxide (98%) was dissolved in 51.5 g ofde-mineralized water in a polypropylene bottle under agitation. To theresulting solution, 27.42 g of a commercial USY powder (Al₂O₃=17.44 wt.%, SiO₂=55.89 wt. %, Na₂O=0.08 wt. %) was added to form a whitehomogeneous slurry. Next, 26.23 g ofN,N-dimethyl-3,5-dimethylpiperidinium hydroxide (R_(A)OH) solution(55.8% aqueous concentration) and then 289.2 g of sodium silicatesolution (Na₂O wt. %=9.00 wt. %, SiO₂=28.8 wt. %) were sequentiallypoured into the mixture. The resulting synthesis gel, corresponding to amolar gel formula of 35.0SiO₂-1.00Al₂O₃-11.0Na₂O-1.50R_(A)OH-300H₂O, waskept for agitation for 30 minutes and then load to a 0.6 L agitatedautoclave for crystallization at 120° C. After 68 hours ofcrystallization, the solid product was recovered and dried in an oven at120° C. The characteristic XRD data of a sample of Example 1 appears inTable 9 below.

TABLE 9 Powder XRD characteristic lines of SDA containing JMZ-11Ahydrated. 2-Theta [°] ^((a)) d-spacing [Å] Rel. Int. [%] 7.7 11.47 1009.6 9.17 8 11.8 7.51 27 13.1 6.74 50 15.2 5.84 27 17.6 5.04 20 18.0 4.9297 20.0 4.44 59 21.0 4.23 19 21.9 4.06 76 22.6 3.93 19 26.2 3.40 59 27.33.27 9 28.1 3.18 22 28.7 3.11 9 30.3 2.95 60 31.0 2.89 23 31.6 2.83 3533.7 2.66 18 34.8 2.58 31 43.7 2.07 16 48.0 1.89 10 ^((a)) = ±0.2; Rel.Int. = I/I₀ × 100; Peaks with Rel. Int. <5% are not listed.

The as-made powder of Example 1 was directly ion exchanged by applying 4cycles of contact with ammonium acetate (10 g of solution for gram ofzeolite powder, 10% 15 ammonium acetate, 80° C. and 1 hour per ionexchange cycle). After drying in an oven at 120° C., direct ionexchanged product was then calcined to remove the SDA species in amuffler furnace by increasing the temperature to 550° C. with a rampingrate of 1.0° C. per minute. After 6 hours of calcination, the resultingpowder was subject to two additional cycles of ion exchange withammonium acetate to remove residual sodium from the zeolite powder.After removing sodium by ion exchange, the solid product was again driedat 120° C. and calcined at 550° C. with the same procedure. The X-raydiffraction data for the product appears in FIG. 1 and Table 10. The SAR(silica to alumina ratio) of the resulting zeolite was 7.1 as measuredby XRF.

TABLE 10 Diffraction peaks of H-JMZ-11A hydrated. 2-Theta [°] ^((a))d-spacing [Å] Rel. Int. [%] 7.7 11.49 31 9.6 9.2 8 11.7 7.53 28 13.16.74 100 15.2 5.84 13 17.6 5.03 8 18.1 4.91 54 20 4.43 33 20.8 4.26 1121.9 4.05 34 22.7 3.92 7 26.2 3.39 38 27.4 3.25 6 28.1 3.17 10 28.7 3.117 30.4 2.94 24 31 2.88 10 31.6 2.83 16 33.8 2.65 5 34.9 2.57 11 43.92.06 5 48.1 1.89 6 ^((a)) = ±0.2; Rel. Int. = I/I₀ × 100; Peaks withRel. Int. <5% are not listed.

Example 2—Synthesis of SDA Containing JMZ-11B with Approximate 65% chaCavities, 5% aft Cavities and 30% “sfw-GME” Tail

13.18 g of sodium hydroxide (98%) was dissolved in 40.0 g ofde-mineralized water in a poly propylene bottle under agitation. To theresulting solution, 28.30 g of a commercial USY powder (Al₂O₃=17.44 wt.%, SiO₂=55.89 wt. %, Na₂O=0.08 wt. %) was added to form a whitehomogeneous slurry. Next, 32.9 g of 1,1-Diethyl-2,6-dimethylpiperidiniumhydroxide solution (22.0% aqueous concentration) and then 288.5 g ofsodium silicate solution (Na₂O wt. %=9.00 wt. %, SiO₂=28.8 wt. %) weresequentially poured into the mixture. The resulting synthesis gel,corresponding to a molar gel formula of34.0SiO₂-1.00Al₂O₃-12.0Na₂O-0.80R_(C)OH-290H₂O, was kept for agitationfor 30 minutes and then load to a 0.6 L agitated autoclave forcrystallization at 120° C. After 21 hours of crystallization, the solidproduct was recovered and dried in an oven at 120° C. The XRD dataappears in Table 11 below.

TABLE 11 Powder XRD characteristic lines of SDA containing JMZ-11Bhydrated. 2-Theta [°] ^((a)) d-spacing [Å] Rel. Int. [%] 7.5 11.71 4210.5 8.43 9 12.9 6.84 55 15 5.9 13 17.8 4.98 100 19.8 4.47 32 21.3 4.1728 21.9 4.05 19 22.5 3.96 17 26 3.42 61 27.1 3.28 8 28 3.18 6 30.2 2.9644 31 2.88 24 31.6 2.83 15 34.6 2.59 32 43.5 2.08 18 47.8 1.9 9 50.8 1.820

The as-made powder of Example 2 was ion-exchanged and calcined asdescribed in Example 1. The X-ray diffraction data for the productappears in FIG. 2 and Table 12. The SAR of the resulting zeolite was 6.2as measured by XRF.

TABLE 12 Diffraction peaks of activated H-JMZ-11B hydrated. 2-Theta [°]^((a)) d-spacing [Å] Rel. Int. [%] 7.6 11.65 20 10.8 8.22 14 13 6.8 10015.1 5.88 9 17.9 4.94 53 19.9 4.45 23 21.4 4.15 16 22.1 4.02 12 22.53.94 8 26.1 3.41 31 27.2 3.27 4 28.1 3.17 4 30.3 2.95 18 31.1 2.87 1131.8 2.81 9 34.7 2.58 9 43.7 2.07 4 48 1.9 4 51 1.79 6

Example 3—Synthesis of SDA Containing JMZ-11C with Approximate 39% chaCavities, 54% aft Cavities and 7% “sfw-GME” Tail

27.35 g of a commercial USY powder (Al₂O₃=17.44 wt. %, SiO₂=55.89 wt. %,Na₂O=0.08 wt. %) was combined with 45.77 g of de-mineralized water in apoly propylene bottle under agitation to form a white homogeneousslurry. To the solution, 24.42 g ofN,N-Dimethyl-3,5-dimethylpiperidinium hydroxide solution (55.8% aqueousconcentration) and 8.29 g of 1,3-bis(1-adamantyl)imidazolium hydroxide(20.0% aqueous concentration) were added. 7.39 g of NaOH (98%) and 288.4g of sodium silicate solution (Na₂O wt. %=9.00 wt. %, SiO₂=28.8 wt. %)were sequentially poured into the mixture. The resulting synthesis gel,corresponding to a molar gel formula of35.0SiO₂-1.00Al₂O₃-11.0Na₂O-1.40R_(A)OH-0.10R_(B)OH-300H₂O, was kept foragitation for 30 minutes and then loaded to a 0.6 L agitated autoclavefor crystallization at 120° C. After 24 hours of crystallization, thesolid product was recovered and dried in an oven at 120° C. The XRD dataappears in Table 13 below.

TABLE 13 Powder XRD characteristic lines of SDA containing JMZ-11Chydrated. 2-Theta [°] ^((a)) d-spacing [Å] Rel. Int. [%] 7.5 11.86 7 8.110.92 6 9.2 9.61 12 11.6 7.62 32 12.9 6.85 100 17.4 5.08 7 17.9 4.95 5019.8 4.47 11 20.5 4.32 14 21.8 4.08 25 22.2 4.01 6 26 3.42 28 28.1 3.188 30.2 2.95 10 30.6 2.92 11 31.5 2.84 11 31.8 2.81 6 34.7 2.58 9

The as-made powder of Example 3 was ion-exchanged and calcined asdescribed in Example 1. The X-ray diffraction data for the productappears in FIG. 4 and Table 14. The SAR of the resulting zeolite was 8.0as measured by XRF.

TABLE 14 Diffraction peaks of activated H-JMZ-11C hydrated. 2-Theta [°]^((a)) d-spacing [Å] Rel. Int. [%] 7.5 11.75 26 8 11.03 12 9.4 9.41 1711.5 7.68 21 12.9 6.86 48 15 5.91 18 15.9 5.57 14 17.4 5.11 24 17.7 5100 19.8 4.48 45 20.6 4.32 41 21.7 4.09 72 22.5 3.96 23 26 3.41 34 27.23.27 7 27.8 3.21 24 28.5 3.13 8 30.2 2.96 47 30.6 2.92 42 31.4 2.85 3733.5 2.68 17 34.6 2.59 34 42.8 2.11 9 43.6 2.08 21

Example 4—Synthesis of SDA Containing JMZ-11D with Approximate 65% chaCavities, 12% aft Cavities and 23% “sfw-GME” Tail

7.27 g of sodium hydroxide (98%) was dissolved in 45.7 g ofde-mineralized water in a poly propylene bottle under agitation. To theresulting solution, 27.41 g of a commercial USY powder (Al₂O₃=17.44 wt.%, SiO₂=55.89 wt. %, Na₂O=0.08 wt. %) was added to form a whitehomogeneous slurry. Next, 26.23 g ofN,N-dimethyl-3,5-dimethylpiperidinium hydroxide solution (55.8% aqueousconcentration), 5.83 g of trimethyladmandylammonium hydroxide (0.51%aqueous concentration) and then 289.2 g of sodium silicate solution(Na₂O wt. %=9.00 wt. %, SiO₂=28.8 wt. %) were sequentially poured intothe mixture. The resulting synthesis gel, corresponding to a molar gelformula of 35.0SiO₂-1.00Al₂O₃-11.0Na₂O-1.50R_(A)OH-0.003R_(B)OH-300H₂O,was kept for agitation for 30 minutes and then load to a 0.6 L agitatedautoclave for crystallization at 120° C. After 64 hours ofcrystallization, the solid product was recovered and dried in an oven at120° C. The XRD data appears in Table 15 below.

TABLE 15 Powder XRD characteristic lines of SDA containing JMZ-11Dhydrated. 2-Theta [°] ^((a)) d-spacing [Å] Rel. Int. [%] 7.6 11.66 259.7 9.1 9 11.6 7.59 25 13 6.79 100 15.1 5.88 12 17.5 5.06 7 17.9 4.95 5019.9 4.45 27 20.8 4.26 9 21.8 4.07 26 22.6 3.93 6 26.1 3.41 33 28 3.19 830.3 2.95 19 30.9 2.89 8 31.6 2.83 12 34.8 2.58 9

The as-made powder of Example 4 was ion-exchanged and calcined asdescribed in Example 1. The X-ray diffraction data for the productappears in FIG. 8 and Table 16. The SAR of the resulting zeolite was 7.3as measured by XRF.

TABLE 16 Diffraction peaks of H-JMZ-11D hydrated. 2-Theta [°] ^((a))d-spacing [Å] Rel. Int. [%] 7.6 11.66 25 9.7 9.1 9 11.6 7.59 25 13 6.79100 15.1 5.88 12 17.5 5.06 7 17.9 4.95 50 19.9 4.45 27 20.8 4.26 9 21.84.07 26 22.2 4 11 26.1 3.4 33 28 3.19 8 30.3 2.95 19 30.9 2.89 8 31.62.83 12 31.8 2.8 8 34.8 2.58 9

Example 5—Preparation of Cu Catalyst for SCR

Calcined JMZ-11A from Example 1, Example 2, Example 3 and Example 4,respectively, were impregnated with copper at a loading of 3.33 wt. %using the required amount of copper (II) acetate monohydrate (Shepherd)dissolved in de-mineralised water. The impregnated samples were driedovernight at 80° C. and then calcined in air at 550° C. for 4 hours. Areference sample of BEA with SAR 28 was prepared following the samemethod described above.

Samples of the powdered catalyst were pelletized to provide the freshcatalyst, and a portion of the fresh catalyst is then hydrothermallyaged in a flow of 10% H₂O in air using the following procedure: thesamples were heated at a rate of 10° C./min to 250° C. in air only. Thesamples were then heated at a rate of 10° C./min in 10% H₂O in air to750° C. After being held at a temperature of 750° C. for 80 hours, thesamples were cooled in the steam/air mixture until then temperature was<250° C., then air only flowed over the samples until they cooled toabout room temperature.

Example 6—Catalyst Testing for Standard NH₃ SCR

Pelletized fresh and aged samples of the powder catalyst were tested inan apparatus in which a gas comprising 500 ppm NO_(x) (NO-only), 500 ppmNH₃, 14% O₂, 4.6% H₂O, 5% CO₂, with the remainder being N₂ flowed overthe catalyst at a space velocity of 90K/h. The samples were heated fromroom temperature to 150° C. under the above mentioned gas mixture exceptfor NH₃. At 150° C., NH₃ was added in to the gas mixture and the sampleswere held under these conditions for 30 min. The temperature was thenincreased (ramped) from 150 to 500° C. at 5° C./minute.

NO_(x) conversion activity profile results are depicted in FIGS. 26 and27 . It has been found that a fresh sample of Example 1 demonstratedNO_(x) conversion levels of 1%-15% higher than the benchmark BEA.Cu inthe temperatures range of 340° C.-550° C. (FIG. 26 ). Example 2, 3, and4 all exhibited NO_(x) conversion levels of 1%-15% higher than thebenchmark BEA.Cu in the temperatures range of 275° C.-550° C. Afteraging, (FIG. 27 ) Example 3 and 4 showed NO_(x) conversion levels of5-65% higher than BEA.Cu across the entire tested temperature range of150-550° C. After aging, Example 1 and 2 exhibited NO_(x) conversionlevels of 2-20% higher than that of BEA.Cu in the temperature range of275-450° C. Therefore, it has been demonstrated that Examples 1, 2, 3,and 4 exhibit significant advantages in NO_(x) conversion when utilizedin the optimal operating temperature range.

The concentration of N₂O in gas passing through fresh and aged catalystsover temperatures from 150° C. to 500° C. are given in FIG. 28 . Gasflowing into the apparatus contained 500 ppm NO_(x) as NO-only. Thelevels of N₂O produced by Examples 1, 2, 3, and 4 were all significantlylower (˜5 ppm peak value) than that of BEA (peak values of −55 ppm and28 ppm) over the entire temperature range. After aging (FIG. 29 ), N₂Olevels produced by BEA significantly decreased over the entiretemperature range exhibiting peak values at ˜11 ppm and ˜18 ppm.However, aged samples of Example 1, 2, 3, and 4 all still produced lowerlevels of N₂O than BEA over the entire temperature range despite theobservation that these samples also exhibited higher NO_(x) conversionover the majority of the temperature range. Thus, Example 1, 2, 3, and 4all exhibit significant advantages in N₂O production over BEA both freshand aged.

What is claimed is:
 1. A molecular sieve comprising a first structuredirecting agent (SDA-1), cha cavities, aft cavities and an “sfw-GME”tail, wherein SDA-1 comprises an N,N-dimethyl-3,5-dimethylpiperidiniumcation or an N,N-diethyl-2,6-dimethylpiperidinium cation, wherein saidmolecular sieve has a framework, and wherein the sfw-GME tail has amonotonically decreasing distribution of cavity sizes.
 2. The molecularsieve of claim 1, wherein SDA-1 comprises anN,N-dimethyl-3,5-dimethylpiperidinium cation, the cha cavities arepresent at about 45 to about 65% of the cavities in the tail, the aftcavities are present at about 18 to about 28% of the cavities in thetail, and the remaining about 7 to about 37% are present as largercavities in the “sfw-GME” tail, and wherein the larger cavities compassa range in cavity sizes from that of the sfw cavities to “infinity”. 3.The molecular sieve of claim 2, wherein the “sfw-GME” tail accounts forabout 35-80% of the volume of the molecular sieve.
 4. The molecularsieve of claim 1, wherein the molecular sieve is an aluminosilicate anda powder XRD pattern of the hydrated aluminosilicate has the followingcharacteristic lines with the corresponding intensities: Rel. 2-Thetad-spacing Int. [°] ^((a)) [Å] [%] 7.7 11.47 vs 9.6 9.17 w 11.8 7.51 m13.1 6.74 s 15.2 5.84 m 17.6 5.04 m 18.0 4.92 vs 20.0 4.44 s 21.0 4.23 w21.9 4.06 vs 22.6 3.93 w 26.2 3.40 s 27.3 3.27 w 28.1 3.18 m 28.7 3.11 w30.3 2.95 s 31.0 2.89 m 31.6 2.83 m 33.7 2.66 w 34.8 2.58 m 43.7 2.07 w48.0 1.89 w ^((a)) = ±0.2, Rel. Int. = I/I0 × 100; Peaks with Rel. Int.<5% are not listed

wherein “Rel Int” is defined as: w (weak)<20; m (medium) is >20 and <40;s (strong) is >40 and <60; and vs (very strong) is >60, compared to themaximum peak height.
 5. The molecular sieve of claim 1, wherein SDA-1comprises an N,N-diethyl-2,6-dimethylpiperidinium cation, the chacavities are present at about 55 to about 75 are present as largercavities in the “sfw-GME” tail, and wherein the larger cavities compassa range in cavity sizes from that of the sfw cavities to “infinity”. 6.The molecular sieve of claim 5, wherein the “sfw-GME” tail accounts forabout 40-80% of the volume of the molecular sieve and the molecularsieve has a monotonically decreasing distribution of cavity sizes. 7.The molecular sieve of claim 1, wherein the molecular sieve is analuminosilicate and a powder XRD pattern of the hydrated aluminosilicatehas the following characteristic lines with the correspondingintensities: Rel. 2-Theta d-spacing Int. [°] ^((a)) [Å] [%] 7.5 11.71m-s 10.5 8.43 w 12.9 6.84 s-vs 15.0 5.90 w 17.8 4.98 vs 19.8 4.47 m 21.34.17 m 21.9 4.05 w-m 22.5 3.96 w-m 26.0 3.42 s-vs 27.1 3.28 w 28.0 3.18w 30.2 2.96 m-s 31.0 2.88 m 31.6 2.83 w 34.6 2.59 m 43.5 2.08 w-m 47.81.90 w ^((a)) = ±0.2, Rel. Int. = I/I0 × 100; Peaks with Rel. Int. <5%are not listed

wherein “Rel Int” is defined as: w (weak)<20; m (medium) is >20 and <40;s (strong) is >40 and <60; and vs (very strong) is >60, compared to themaximum peak height.
 8. The molecular sieve of claim 1, wherein SDA-1comprises an N,N-dimethyl-3,5-dimethylpiperidinium cation and themolecular sieve further comprises a 1,3-bis(1-adamantyl)imidazoliumcation, wherein the cha cavities are present at about 30 to about 45% ofthe cavities in the tail, the aft cavities are present at about 45 toabout 65% of the cavities in the tail, and the remaining about 2 toabout 20% are present as larger cavities in the “sfw-GME” tail, andwherein the larger cavities compass the range in cavity sizes from thatof the sfw cavities to “infinity”.
 9. The molecular sieve of claim 8,wherein the “sfw-GME” tail accounts for about 5-45% of the volume of themolecular sieve.
 10. The molecular sieve of claim 1, wherein themolecular sieve is an aluminosilicate and a powder XRD pattern of thehydrated aluminosilicate has the following characteristic lines with thecorresponding intensities: Rel. 2-Theta d-spacing Int. [°] ^((a)) [Å][%] 7.5 11.86 w 8.1 10.92 w 9.2 9.61 w 11.6 7.62 m 12.9 6.85 vs 17.45.08 w 17.9 4.95 s 19.8 4.47 w 20.5 4.32 w 21.8 4.08 m 22.2 4.01 w 26.03.42 m 28.1 3.18 w 30.2 2.95 w 30.6 2.92 w 31.5 2.84 w 31.8 2.81 w 34.72.58 w ^((a)) = ±0.2, Rel. Int. = I/I/0 × 100; Peaks with Rel. Int. <5%are not listed

wherein “Rel Int” is defined as: w (weak)<20; m (medium) is >20 and <40;s (strong) is >40 and <60; and vs (very strong) is >60, compared to themaximum peak height.
 11. The molecular sieve of claim 1, wherein SDA-1comprises an N,N-dimethyl-3,5-dimethylpiperidinium cation and themolecular sieve further comprises a trimethyladmandylammonium cation,wherein the cha cavities are present at about 55 to about 75% of thecavities in the tail, the aft cavities are present at about 7 to about17% of the cavities in the tail, and the remaining about 8 to about 38%are present as larger cavities in the “sfw-GME” tail, and wherein alarger cavities compass the range in cavity sizes from that of the sfwto “infinity”.
 12. The molecular sieve of claim 11, wherein the“sfw-GME” tail accounts for about 50-90% of the volume of the molecularsieve.
 13. The molecular sieve of claim 1, wherein the molecular sieveis an aluminosilicate and a powder XRD pattern of the hydratedaluminosilicate has the following characteristic lines with thecorresponding intensities: Rel. 2-Theta d-spacing Int. [°] ^((a)) [Å][%] 7.6 11.66 m 9.7 9.1 w 11.6 7.59 m 13 6.79 vs 15.1 5.88 w 17.5 5.06 w17.9 4.95 s 19.9 4.45 m 20.8 4.26 w 21.8 4.07 m 22.6 3.93 w 26.1 3.41 m28 3.19 w 30.3 2.95 w-m 30.9 2.89 w 31.6 2.83 w 34.8 2.58 w ^((a)) =±0.2, Rel. Int. = I/I0 × 100; Peaks with Rel. Int. <5% are not listed

wherein “Rel Int” is defined as: w (weak)<20; m (medium) is >20 and <40;s (strong) is >40 and <60; and vs (very strong) is >60, compared to themaximum peak height.
 14. The molecular sieve of claim 1, wherein themolecular sieve has a monotonically decreasing distribution of cavitysizes.
 15. An activated molecular sieve comprising cha cavities, aftcavities and an “sfw-GME” tail, wherein the molecular sieve does notcomprise an SDA, wherein said molecular sieve has a framework, andwherein the sfw-GME tail has a monotonically decreasing distribution ofcavity sizes.
 16. The activated molecular sieve of claim 15, wherein thecha cavities are present at about 45 to about 65% of the cavities in thetail, the aft cavities are present at about 18 to about 28% of thecavities in the tail, and the remaining about 7 to about 37% are presentas larger cavities in the “sfw-GME” tail, and wherein the largercavities compass a range in cavity sizes from that of the sfw cavitiesto “infinity”.
 17. The activated molecular sieve of claim 16, whereinthe “sfw-GME” tail accounts for about 35-80% of the volume of themolecular sieve.
 18. The activated molecular sieve of claim 15, whereinthe molecular sieve is an aluminosilicate and a powder XRD pattern ofthe hydrated aluminosilicate has the following characteristic lines withthe corresponding intensities: Rel. 2-Theta d-spacing Int. [°] ^((a))[Å] [%] 7.7 11.49 m 9.6 9.20 w 11.7 7.53 m 13.1 6.74 vs 15.2 5.84 w 17.65.03 w 18.1 4.91 s 20.0 4.43 m 20.8 4.26 w 21.9 4.05 m 22.7 3.92 w 26.23.39 m 27.4 3.25 w 28.1 3.17 w 28.7 3.11 w 30.4 2.94 m 31.0 2.88 w 31.62.83 w 33.8 2.65 w 34.9 2.57 w 43.9 2.06 w 48.1 1.89 w ^((a)) = ±0.2,

wherein “Rel Int” is defined as: w (weak)<20; m (medium) is >20 and <40;s (strong) is >40 and <60; and vs (very strong) is >60, compared to themaximum peak height.
 19. The activated molecular sieve of claim 15,wherein the cha cavities are present at about 55 to about 75% of thecavities in the tail, and the remaining about 15 to about 45% arepresent as larger cavities in the “sfw-GME” tail, and wherein the largercavities compass a range in cavity sizes from that of the sfw cavitiesto “infinity”.
 20. The activated molecular sieve of claim 19, whereinthe “sfw-GME” tail accounts for about 40-80% of the volume of themolecular sieve and the molecular sieve has a monotonically decreasingdistribution of cavity sizes.
 21. The activated molecular sieve of claim15, wherein the molecular sieve is an aluminosilicate and a powder XRDpattern of the dehydrated aluminosilicate has the followingcharacteristic lines with the corresponding intensities: Rel. 2-Thetad-spacing Int. [°] ^((a)) [Å] [%] 7.6 11.65 w-m 10.8 8.22 w 13.0 6.80 vs15.1 5.88 w 17.9 4.94 s 19.9 4.45 w-m 21.4 4.15 w-m 22.1 4.02 w 22.53.94 w 26.1 3.41 m 27.2 3.27 w 28.1 3.17 w 30.3 2.95 w-m 31.1 2.87 w31.8 2.81 w 34.7 2.58 w 43.7 2.07 w 48.0 1.90 w ^((a)) = ±0.2, Rel. Int.= I/I0 × 100; Peaks with Rel. Int. <5% are not listed

wherein “Rel Int” is defined as: w (weak)<20; m (medium) is >20 and <40;s (strong) is >40 and <60; and vs (very strong) is >60, compared to themaximum peak height.
 22. The activated molecular sieve of claim 15,wherein the cha cavities are present at about 30 to about 45% of thecavities in the tail, the aft cavities are present at about 45 to about65% of the cavities in the tail, and the remaining about 2 to about 20%are present as larger cavities in the “sfw-GME” tail, and wherein thelarger cavities compass a range in cavity sizes from that of the sfw to“infinity”.
 23. The activated molecular sieve of claim 22, wherein the“sfw-GME” tail accounts for about 5-45% of the volume of the molecularsieve.
 24. The activated molecular sieve of claim 15, wherein themolecular sieve is an aluminosilicate and a powder XRD pattern of thedehydrated aluminosilicate has the following characteristic lines withthe corresponding intensities: Rel. 2-Theta d-spacing Int. [°] ^((a))[Å] [%] 7.5 11.75 m 8.0 11.03 w 9.4 9.41 w 11.5 7.68 w-m 12.9 6.86 s15.0 5.91 w-m 15.9 5.57 w 17.4 5.11 m 17.7 5.00 vs 19.8 4.48 s 20.6 4.32m-s 21.7 4.09 vs 22.5 3.96 w-m 26.0 3.41 m 27.2 3.27 w 27.8 3.21 m 28.53.13 w 30.2 2.96 s 30.6 2.92 s 31.4 2.85 m-s 33.5 2.68 w 34.6 2.59 m42.8 2.11 w 43.6 2.08 w-m ^((a)) = ±0.2, Rel. Int. = I/I0 × 100; Peakswith Rel. Int. <5% are not listed

wherein “Rel Int” is defined as: w (weak)<20; m (medium) is >20 and <40;s (strong) is >40 and <60; and vs (very strong) is >60, compared to themaximum peak height.
 25. The activated molecular sieve of claim 15,wherein the cha cavities are present at about 55 to about 75% of thecavities in the tail, the aft cavities are present at about 7 to about17% of the cavities in the tail, and the remaining about 8 to about 38%are present as larger cavities in the “sfw-GME” tail, and wherein thelarger cavities compass a range in cavity sizes from that of the sfwcavities to “infinity”.
 26. The activated molecular sieve of claim 25,wherein the “sfw-GME” tail accounts for about 50-90% of the volume ofthe molecular sieve.
 27. The activated molecular sieve of claim 15,wherein the molecular sieve is an aluminosilicate and a powder XRDpattern of the dehydrated aluminosilicate has the followingcharacteristic lines with the corresponding intensities: Rel. 2-Thetad-spacing Int. [°] ^((a)) [Å] [%] 7.6 11.66 m 9.7 9.10 w 11.6 7.59 m13.0 6.79 vs 15.1 5.88 w 17.5 5.06 w 17.9 4.95 s 19.9 4.45 m 20.8 4.26 w21.8 4.07 m 22.2 4.00 w 26.1 3.40 m 28.0 3.19 w 30.3 2.95 w-m 30.9 2.89w 31.6 2.83 w 31.8 2.80 w 34.8 2.58 w ^((a)) = ±0.2, Rel. Int. = I/I0 ×100; Peaks with Rel. Int. <5% are not listed

wherein “Rel Int” is defined as: w (weak)<20; m (medium) is >20 and <40;s (strong) is >40 and <60; and vs (very strong) is >60, compared to themaximum peak height.
 28. The activated molecular sieve of claim 15,wherein the molecular sieve has a monotonically decreasing distributionof cavity sizes.
 29. The molecular sieve of claim 1, where the molecularsieve is an aluminosilicate or a metal-substituted aluminosilicate,wherein the metal is substituted into the framework of the molecularsieve.
 30. The molecular sieve of claim 1, wherein the molecular sieveis an aluminosilicate having a silica to alumina ratio (SAR) of 20 orless.
 31. The molecular sieve of claim 1, where the molecular sievecomprises phosphorus in the framework.
 32. The molecular sieve of claim1, where the molecular sieve comprises at least one metal within theframework where the metal is selected from at least one of the metals ofgroups IIIA, IB, IIB, VA, VIA, VIIA, and VIIIA of Groups of the PeriodicTable and combinations thereof.
 33. The activated molecular sieve ofclaim 15, where the molecular sieve further comprises at least oneextra-framework metal selected from the group consisting of Ag, Au, Ce,Co, Cr, Cu, Fe, Ga, In, Jr, Mn, Mo, Ni, Os, Pd, Pt, Re, Rh, Ru, Sn andZn.
 34. The activated molecular sieve of claim 15, where the molecularsieve further comprises at least one extra-framework metal selected fromthe group consisting of Ag, Au, Jr, Os, Pd, Pt, Rh and Ru.
 35. Acatalyst comprising the activated molecular sieve of claim
 15. 36. Thecatalyst of claim 35, wherein the activated molecular sieve comprisesabout 0.1 to about 5 weight percent of at least one extra-frameworkmetal.
 37. The catalyst of claim 35, wherein the activated molecularsieve comprises about 0.1 to about 5 weight percent ionic copper.
 38. Acatalyst article for treating exhaust gas comprising a catalyst of claim35, where the catalyst is disposed on and/or within a honeycombstructure.
 39. A method for treating an exhaust gas comprisingcontacting a combustion exhaust gas containing NO_(x) and/or NH₃ withthe activated molecular sieve according to claim 15 to selectivelyreduce at least a portion of the NO_(x) into N₂ and H₂O and/or oxidizeat least a portion of the NH₃.
 40. A method for treating an exhaust gascomprising contacting a combustion exhaust gas containing NO_(x) with apassive NOx absorber comprising the activated molecular sieve of claim15.
 41. A method for treating an exhaust gas comprising contacting acombustion exhaust gas containing NO_(x) with a passive NOx absorbercomprising the activated molecular sieve of claim
 15. 42. A method ofconverting methanol to an olefin (MTO), the method comprising contactingmethanol with the activated molecular sieve of claim 15.